Fluorine-containing cyclic olefin polymer composition, imprint product obtained using the composition, and method for producing the same

ABSTRACT

A fluorine-containing cyclic olefin polymer composition of the present invention includes a fluorine-containing cyclic olefin polymer (A) containing a repeating structural unit represented by the general formula (1) and having a fluorine atom content rate of 40 to 75% by mass; a photocurable compound (B); and a photocuring initiator (C).

TECHNICAL FIELD

The present invention relates to a fluorine-containing cyclic olefinpolymer composition, an imprint product having a desired fine patternformed using the composition, and a method for producing the same.

BACKGROUND ART

A resin molding product having a fine pattern is useful such as anoptical element (a micro lens array, an optical waveguide, an opticalswitching, a Fresnel zone plate, a binary optical element, a blazeoptical element, a photonics crystal, or the like), an anti-reflectionfilter, a biochip, a microreactor chip, a recording medium, a displaymaterial, a carrier for a catalyst. There has been recently a demand foracquisition of smaller devices as well as finer patterns thereof. As amethod for preparing a resin molding product having such a finestructure over its surface, there has been proposed a method in which apattern of a mold having a fine pattern is transcribed on a resin toproduce an imprint product having a fine pattern formed thereon, thatis, a so-called nanoimprint method (see, for example, Patent Documents 1and 2). Furthermore, as a method substituting for a photolithographicmethod in a process of manufacturing semiconductor, there has beenproposed a nanoimprint method in which a resist is coated on a siliconesubstrate and a mold having a fine pattern formed thereon is pressed totranscribe the fine pattern on the resist (see, for example, PatentDocuments 3 and 4).

However, in any of the above-mentioned nanoimprint methods, a step ofreleasing a mold has suffered from a problem that the mold is notsmoothly released and the shape precision of fine patterns in theimprint product is reduced. Thus, in order to smoothly release the mold,an attempt has been made to coat a release agent on a mold surface. Inthis case, there have been problems that unevenness in the thickness ofa release agent layer causes reduction of the pattern precision of amold, and that the release agent layer becomes thinner due to successiveuse of the mold, and accordingly, there occurs a need to coat a releaseagent on the mold again, leading to reduction of the productivity.

In order to solve these problems, there has been proposed a method inwhich a non-adhesive material having a non-adhesive surface energy ofless than about 30 dyn/cm is used as a mold material (Patent Document5). Examples of the non-adhesive material include fluoropolymers such asa fluorinated ethylene propylene copolymer, a tetrafluoroethylenepolymer; fluorinated siloxane polymers; silicones; and the like.

However, the method described in Patent Document 5 includes imprinting amold or its negative pattern made of a non-adhesive material onto aphotocurable or thermosetting thin film formed on a substrate. that is,the method uses a mold or its negative pattern as a lithographic tool.In Patent Document 5, the non-adhesive material is intended to servemainly as a release agent. Further, a mold using silicone has a lowelastic modulus, and it is difficult to imprint a pattern shapeprecisely.

Furthermore, in Patent Document 6, there is disclosed a method forforming a pattern on a transcription layer, which consists of a step inwhich a thermoplastic resin containing a fluorine-containing polymerwhich has 35% by mass or more of a fluorine content, is pressed with amold having an inverse pattern of a desired pattern, and thereby forminga desired pattern on the transcription layer; and a step in which themold is released from the transcription layer. It is described thataccording to this method, the releasability of the transcription layeris excellent and a fine pattern can be formed. Herein, examples of thefluorine-containing 1 polymer include polytetrafluoroethylene, a1,1,1-trifluoro-2-trifluoromethylpenten-2-ol copolymer, aperfluorocyclic ether polymer (trade name CYTOP®), a copolymer ofchlorotrifluoroethylene and vinyl ether (trade name LUMIFLON®), and thelike.

However, when the fluorine content of these polymers is 60% by mass orless, their dimensional accuracy in terms of the depth, width andinterval of convex structures is low and dimensional difference islarge, because the elastic modulus is rapidly decreased at a temperatureabove the glass transition temperature, and after the polymer issubjected to press molding, when cooling rapidly, the shrinkage ratio isincreased due to the decreased elastic modulus. In addition, even iffluorine content is 60% by mass or more, the fluorine resins such aspolytetrafluoroethylene which exhibit a high melting point temperature(Tm), since it is necessary to set the molding temperature markedlyhigher, provide significant differences in the dimensions between theconvex structure mold and the imprint product because of increase in thedifferences between the elastic modulus and shrinkage ratio during theprocess of heating and cooling. Furthermore, the fluorine resins must bepressed at temperature of 300° C. or higher which associate with a highpossibility of decomposition of the fluorine resins when heated at thetemperature of 260° C. higher to generate hydrogen fluoride gas andtherefore, there occur problems such as corrosion of molds andperipheral devices, environmental pollution.

The imprint methods which comprise molding by heat press as suggested asdescribed above, are required to uniformly put high pressure on a largearea in order to obtain an imprint product with a large area, and thus alarge-sized heat press molding machine is necessitated. Thus, there is alarge problem in manufacturing an imprint product with a large areabecause of limitations on the area of the imprint product that can beindustrially processed.

RELATED DOCUMENT Patent Document

[Patent Document 1] PCT Japanese Translation Patent Publication No.2004-504718

[Patent Document 2] PCT Japanese Translation Patent Publication No.2002-539604

[Patent Document 3] Japanese Unexamined Patent Publication No.2000-323461

[Patent Document 4] Japanese Unexamined Patent Publication No.2003-155365

[Patent Document 5] PCT Japanese Translation Patent Publication No.2005-515617

[Patent Document 6] Japanese Unexamined Patent Publication No.2006-54300

DISCLOSURE OF THE INVENTION

It is an object of the present invention to provide an imprint product,to which a fine pattern on a mold surface is transcribed with highdimensional precision by optimizing the change in the modulus and theshrinkage rate of a resin in the processes of heating, cooling, andcuring with light irradiation in the step for producing a nanoimprintproduct, using a fluorine-containing cyclic olefin polymer compositioncontaining a specific fluorine-containing cyclic olefin polymer, aphotocurable compound, and a photocuring initiator. It is another objectof the present invention to provide an imprint product having a highsurface hardness, using the fluorine-containing cyclic olefin polymercomposition. It is still another object of the present invention toprovide a method for producing an imprint product, in which an imprintcan be efficiently produced with high dimensional precision, and thus,an imprint having a large area can be obtained by a simple process; anda method for preparing a cured product having a fine pattern transcribedto the surface of a photocuring resin using the imprint product as areplica mold.

Means for Solving the Problems

Embodiments of the present invention are as follows.

(1) A fluorine-containing cyclic olefin polymer composition, wherein thecomposition comprises:

a fluorine-containing cyclic olefin polymer (A) containing a repeatingstructural unit represented by the general formula (1) and having afluorine atom content rate of 40 to 75% by mass; a photocurable compound(B); and a photocuring initiator (C).

(in the formula (1), at least one of R¹ to R⁴ is fluorine,fluorine-containing alkyl having 1 to 10 carbon atoms,fluorine-containing alkoxy having 1 to 10 carbon atoms, orfluorine-containing alkoxyalkyl having 2 to 10 carbon atoms. In the casewhere R¹ to R⁴ are fluorine-free groups, R¹ to R⁴ are selected fromhydrogen, alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10carbon atoms, and alkoxyalkyl having 2 to 10 carbon atoms. R¹ to R⁴ maybe the same as or different from each other; R¹ to R⁴ may be combinedwith one another to form a ring structure.)

(2) The fluorine-containing cyclic olefin polymer composition as setforth in (1),

wherein the mass ratio (A)/(B) of the fluorine-containing cyclic olefinpolymer (A) and the photocurable compound (B) is in the range from99.9/0.1 to 80/20.

(3) The fluorine-containing cyclic olefin polymer composition as setforth in (1) or (2),

wherein the photocurable compound (B) is a (meth)acrylate monomer havinga trifunctional or higher reactive double bond group and/or an epoxymonomer having a trifunctional or higher cationically ring-openingpolymerizable linking group.

(4) The fluorine-containing cyclic olefin polymer composition as setforth in any one of (1) to (3),

wherein the storage modulus or loss modulus of the fluorine-containingcyclic olefin polymer (A) in the measurement of a dynamic mechanicalanalysis by tensile mode at a frequency of 1 Hz and a temperatureincrease rate of 3° C./minute has a variable region in the range from −1to 0 MPa/° C. with respect to a temperature varying in the temperatureregion of the glass transition temperature or higher.

(5) The fluorine-containing cyclic olefin polymer composition as setforth in any one of (1) to (4),

wherein the variable region of the storage modulus or loss modulus inthe temperature region of the glass transition temperature or higher ofthe fluorine-containing cyclic olefin polymer (A) is in the storagemodulus region or loss modulus region of 0.1 MPa or more.

(6) The fluorine-containing cyclic olefin polymer composition as setforth in any one of (1) to (5),

wherein the fluorine-containing cyclic olefin polymer (A) is constitutedwith a repeating structural unit [I] represented by the general formula(1) and a repeating structural unit [II] represented by the generalformula (2), the molar ratio thereof is [I]/[II]=95/5 to 25/75, and thefluorine atom content rate is 40 to 75% by mass.

(in the formula (2), at least one of R⁵ to R⁸ is fluorine,fluorine-containing alkyl having 1 to 10 carbon atoms,fluorine-containing alkoxy having 1 to 10 carbon atoms, orfluorine-containing alkoxyalkyl having 2 to 10 carbon atoms. In the casewhere R⁵ to R⁸ are fluorine-free groups, R⁵ to R⁸ are selected fromhydrogen, alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10carbon atoms, and alkoxyalkyl having 2 to 10 carbon atoms. R⁵ to R⁸ maybe the same as or different from each other; R⁵ to R⁸ may be combinedwith one another to form a ring structure; n represents an integer of 1or 2.)

(7) An imprint product having a fine pattern of a mold surfacetranscribed thereon, wherein the imprint product comprises afluorine-containing cyclic olefin polymer (A) containing a repeatingstructural unit represented by the general formula (1) and having afluorine atom content rate of 40 to 75% by mass; a photocurable compound(B); and a photocuring initiator (C).

(in the formula (1), at least one of R¹ to R⁴ is fluorine,fluorine-containing alkyl having 1 to 10 carbon atoms,fluorine-containing alkoxy having 1 to 10 carbon atoms, orfluorine-containing alkoxyalkyl having 2 to 10 carbon atoms; in the casewhere R¹ to R⁴ are fluorine-free groups, R¹ to R⁴ are selected fromhydrogen, alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10carbon atoms, and alkoxyalkyl having 2 to 10 carbon atoms; R¹ to R⁴ maybe the same as or different from each other; R¹ to R⁴ may be combinedwith one another to form a ring structure.)

(8) The imprint product as set forth in (7),

wherein the mass ratio (A)/(B) of the fluorine-containing cyclic olefinpolymer (A) and the photocurable compound (B) is in the range from99.9/0.1 to 80/20.

(9) The imprint product as set forth in (7) or (8),

wherein the storage modulus or loss modulus of the fluorine-containingcyclic olefin polymer (A) in the measurement of a dynamic mechanicalanalysis by tensile mode at a frequency of 1 Hz and a temperatureincrease rate of 3° C./minute has a variable region in the range from −1to 0 MPa/° C. with respect to a temperature varying in the temperatureregion of the glass transition temperature or higher.

(10) The imprint product as set forth in any one of (7) to (9),

wherein the variable region of the storage modulus or loss modulus inthe temperature region of the glass transition temperature or higher ofthe fluorine-containing cyclic olefin polymer (A) is in the storagemodulus region or loss modulus region of 0.1 MPa or more.

(11) The imprint product as set forth in any one of (7) to (10),

wherein the fluorine-containing cyclic olefin polymer (A) is constitutedwith a repeating structural unit [I] represented by the general formula(1) and a repeating structural unit [11] represented by the generalformula (2), the molar ratio thereof is [I]/[II]=95/5 to 25/75, and thefluorine atom content rate is 40 to 75% by mass.

(in the formula (2), at least one of R⁵ to R⁸ is fluorine,fluorine-containing alkyl having 1 to 10 carbon atoms,fluorine-containing alkoxy having 1 to 10 carbon atoms, orfluorine-containing alkoxyalkyl having 2 to 10 carbon atoms; in the casewhere R⁵ to R⁸ are fluorine-free groups, R⁵ to R⁸ are selected fromhydrogen, alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10carbon atoms, and alkoxyalkyl having 2 to 10 carbon atoms; R⁵ to R⁸ maybe the same as or different from each other; R⁵ to R⁸ may be combinedwith one another to form a ring structure; n represents an integer of 1or 2.)

(12) A method for producing an imprint product to which a fine patternof a mold is transcribed, wherein the method comprises a step ofbringing the fluorine-containing cyclic olefin polymer composition asset forth in any one of (1) to (6) into contact with the surface of amold having a fine pattern over its surface, and

a step of heating the composition and then irradiating it with light tocure the composition.

(13) The method for producing an imprint as set forth in (12),

wherein the step of bringing the fluorine-containing cyclic olefinpolymer composition into contact with the surface of the mold comprisesa step of coating the composition over the surface of a mold having afine pattern over its surface.

(14) A method for producing an imprint product to which a fine patternof a mold is transcribed, wherein the method comprises a step of formingthe coating film by coating the fluorine-containing cyclic olefinpolymer composition as set forth in any one of (1) to (6) over asupport,

a step of pressing the upper surface of the coating film to a moldsurface having a fine pattern, and

a step of heating the coating film pressed over the mold surface, andthen irradiating it with light to cure the coating film.

(15) A method for producing a cured body using the imprint product asset forth in any one of (7) to (11) as a mold, wherein the methodcomprises a step of bringing a surface having the fine pattern of animprint product into contact with a photocurable monomer composition,

a step of curing the photocurable monomer composition with lightirradiation to obtain a cured product, and

a step of releasing the cured product from the imprint product.

(16) A resin composition for obtaining an imprint product transcribed afine pattern of a mold surface, wherein the composition comprises afluorine-containing cyclic olefin polymer (A) containing a repeatingstructural unit represented by the general formula (1) and having afluorine atom content rate of 40 to 75% by mass; a photocurable compound(B); and a photocuring initiator (C).

(in the formula (1), at least one of R¹ to R⁴ is fluorine,fluorine-containing alkyl having 1 to 10 carbon atoms,fluorine-containing alkoxy having 1 to 10 carbon atoms, orfluorine-containing alkoxyalkyl having 2 to 10 carbon atoms; in the casewhere R¹ to R⁴ are fluorine-free groups, R¹ to R⁴ are selected fromhydrogen, alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10carbon atoms, and alkoxyalkyl having 2 to 10 carbon atoms; R¹ to R⁴ maybe the same as or different from each other; R¹ to R⁴ may be combinedwith one another to form a ring structure.)

(17) The resin composition for transcription as set forth in (16),

wherein the mass ratio (A)/(B) of the fluorine-containing cyclic olefinpolymer (A) and the photocurable compound (B) is in the range from99.9/0.1 to 80/20.

(18) The resin composition for transcription as set forth in (16) or(17),

wherein the storage modulus or loss modulus of the fluorine-containingcyclic olefin polymer (A) in the measurement of a dynamic mechanicalanalysis by tensile mode at a frequency of 1 Hz and a temperatureincrease rate of 3° C./minute has a variable region in the range from −1to 0 MPa/° C. with respect to a temperature varying in the temperatureregion of the glass transition temperature or higher.

(19) The resin composition for transcription as set forth in any one of(16) to (18),

wherein the variable region of the storage modulus or loss modulus inthe temperature region of the glass transition temperature or higher ofthe fluorine-containing cyclic olefin polymer (A) is in the storagemodulus region or loss modulus region of 0.1 MPa or more.

(20) The resin composition for transcription as set forth in any one of(16) to (19),

wherein the fluorine-containing cyclic olefin polymer (A) is constitutedwith a repeating structural unit [I] represented by the general formula(1) and a repeating structural unit [II] represented by the generalformula (2), the molar ratio thereof is [I]/[II]=95/5 to 25/75, and thefluorine atom content rate is 40 to 75% by mass.

(in the formula (2), at least one of R⁵ to R⁸ is fluorine,fluorine-containing alkyl having 1 to 10 carbon atoms,fluorine-containing alkoxy having 1 to 10 carbon atoms, orfluorine-containing alkoxyalkyl having 2 to 10 carbon atoms; in the casewhere R⁵ to R⁸ are fluorine-free groups, R⁵ to R⁸ are selected fromhydrogen, alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10carbon atoms, and alkoxyalkyl having 2 to 10 carbon atoms; R⁵ to R⁸ maybe the same as or different from each other; R⁵ to R⁸ may be combinedwith one another to form a ring structure; n represents an integer of 1or 2.)

In the present invention, the fine pattern means a structure including aconvex portion and a concave portion, in which the width of the convexportion and/or the concave portion is from 10 nm to 50 μm, the depth ofthe concave portion is from 30 nm to 50 μm, and the aspect ratio of thewidth of the convex portion to the depth of the concave portion is from0.1 to 500.

In the present invention, the expression “bringing a solution includinga polymer composition and an organic solvent into contact with thesurface of a mold having a fine pattern over its surface” includes anyof a case where a solution including a polymer composition and anorganic solvent is coated on a mold surface having a fine pattern formedthereon and a case where the solution is coated over a support (basematerial), and then the upper surface of the coating layer is pressed ona mold surface having a fine pattern formed thereon. In addition, thisshall apply to the expression “bringing a surface having the finepattern of the imprint product into contact with the photocurablemonomer composition”.

Effects of the Invention

According to the present invention, since a specific fluorine-containingcyclic olefin polymer having a hydrocarbon structure in the main chainand a fluorine-containing aliphatic ring structure in the side chain isused, a hydrogen bond can be formed between the molecules or within themolecule. Further, since a photocurable compound and a photocuringinitiator are used, light is irradiated for curing, and thus, athree-dimensional network structure can be formed inside the imprintproduct and over the surface of the imprint product. By such anoperation, it is possible to optimize the change in the modulus and theshrinkage rate of a resin in the processes of heating, cooling, andcuring with light irradiation in the step for preparing a nanoimprintproduct, while further improving the hardness. Therefore, with thefluorine-containing cyclic olefin polymer composition containing aphotocurable compound and a photopolymerization initiator of the presentinvention, the fine pattern of the mold surface is transcribed with highdimensional precision, and as a result, an imprint product having a finepattern over its surface, having a high surface hardness, can be formedand an imprint product having a large area can be obtained by a simpleprocess. This imprint product has an excellent separating property,superior production efficiency, and a high industrial value.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a change in the dynamic viscoelastic modulus measured in atensile mode of the fluorine-containing cyclic olefin polymer obtainedin Example 1, having a flat variable region of the storage modulus orthe loss modulus in a temperature region from 113° C. to 152° C.

DESCRIPTION OF EMBODIMENTS

The fluorine-containing cyclic olefin polymer composition (resincomposition for transcription) of the present invention contains afluorine-containing cyclic olefin polymer (A), a photocurable compound(B), and a photocuring initiator (C).

<Fluorine-Containing Cyclic Olefin Polymer (A)>

The fluorine-containing cyclic olefin polymer (A) contains a repeatingstructural unit represented by the general formula (1) and has afluorine atom content rate of 40 to 75% by mass.

In the formula (1), at least one of R¹ to R⁴ is fluorine,fluorine-containing alkyl having 1 to 10 carbon atoms,fluorine-containing alkoxy having 1 to 10 carbon atoms, orfluorine-containing alkoxyalkyl having 2 to 10 carbon atoms. In the casewhere R¹ to R⁴ are fluorine-free groups, R¹ to R⁴ are selected fromhydrogen, alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10carbon atoms, and alkoxyalkyl having 2 to 10 carbon atoms. R¹ to R⁴ maybe the same as or different from each other. R¹ to R⁴ may be combinedwith one another to form a ring structure.

More specifically, in the general formula (1), examples of R¹ to R⁴include fluorine; or alkyl having 1 to 10 carbon atoms, in which apartor all of hydrogen atoms of the alkyl group is (are) substituted withfluorine atom(s), such as fluoromethyl, difluoromethyl, trifluoromethyl,trifluoroethyl, pentafluoroethyl, heptafluoropropyl,hexafluoroisopropyl, heptafluoroisopropyl, hexafluoro-2-methylisopropyl,perfluoro-2-methylisopropyl, n-perfluorobutyl, n-perfluoropentyl,perfluorocyclopentyl, and the like; alkoxy having 1 to 10 carbon atomsin which a part or all of hydrogen atoms of the alkoxy group is (are)substituted with fluorine atom(s), such as fluoromethoxy,difluoromethoxy, trifluoromethoxy, trifluoroethoxy, pentafluoroethoxy,heptafluoropropoxy, hexafluoroisopropoxy, heptafluoroisopropoxy,hexafluoro-2-methylisopropoxy, perfluoro-2-methylisopropoxy,n-perfluorobutoxy, n-perfluoropentoxy, perfluorocyclopentoxy, and thelike; and alkoxyalkyl having 2 to 10 carbon atoms in which a part or allof hydrogen atoms of the alkoxy group is (are) substituted with fluorineatom(s), such as fluoromethoxymethyl, difluoromethoxymethyl,trifluoromethoxymethyl, tri fluoroethoxymethyl, pentafluoroethoxymethyl,heptafluoropropoxymethyl, hexafluoroisopropoxymethyl,heptafluoroisopropoxymethyl, hexafluoro-2-methylisopropoxymethyl,perfluoro-2-methylisopropoxymethyl, n-perfluorobutoxymethyl,n-perfluoropentoxymethyl, perfluorocyclopentoxymethyl, and the like.

Furthermore, R¹ to R⁴ may be combined with one another to form a ringstructure or to form a ring such as perfluorocycloalkyl,perfluorocycloether, which is formed through oxygen, and the like.

Furthermore, examples of other R¹ to R⁴ containing no fluorine includehydrogen, or alkyl having 1 to 10 carbon atoms, for example, alkyl suchas methyl, ethyl, propyl, isopropyl, 2-methylisopropyl, n-butyl,n-pentyl, cyclopentyl, and the like; alkoxy having 1 to 10 carbon atoms,such as methoxy, ethoxy, propoxy, butoxy, pentoxy, and the like; andalkoxyalkyl having 2 to 10 carbon atoms, such as methoxymethyl,ethoxymethyl, propoxymethyl, butoxymethyl, pentoxymethyl, and the like.

In the present invention, the fluorine-containing cyclic olefin polymer(A) may be a repeating structural unit represented by the generalformula (1) individually or a combination of two or more structuralunits, in which at least one of R′ to R⁴ of the general formula (1) isdifferent from the others.

Furthermore, in the present invention, specific examples of thefluorine-containing cyclic olefin polymer (A) containing the repeatingstructural unit represented by the general formula (1) includepoly(1-fluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene),poly(1-fluoro-1-trifluoromethyl-3,5-cyclopentylene ethylene),poly(1-methyl-1-fluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene),poly(1,1-difluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene),poly(1,2-difluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene),poly(1-perfluoroethyl-3,5-cyclopentylene ethylene),poly(1,1-bis(trifluoromethyl)-3,5-cyclopentylene ethylene),poly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene),poly(1,2-bis(trifluoromethyl)-3,5-cyclopentylene ethylene),poly(1-perfluoropropyl-3,5-cyclopentylene ethylene),poly(1-methyl-2-perfluoropropyl-3,5-cyclopentylene ethylene),poly(1-butyl-2-perfluoropropyl-3,5-cyclopentylene ethylene),poly(1-perfluoro-iso-propyl-3,5-cyclopentylene ethylene),poly(1-methyl-2-perfluoro-iso-propyl-3,5-cyclopentylene ethylene),poly(1,2-difluoro-1,2-bis(trifluoromethyl)-3,5-cyclopentylene ethylene),poly(1,1,2,2,3,3,3a,6a-octafluorocyclopentyl-4,6-cyclopentyleneethylene),poly(1,1,2,2,3,3,4,4,3a,7a-decafluorocyclohexyl-5,7-cyclopentyleneethylene), poly(1-perfluorobutyl-3,5-cyclopentylene ethylene),poly(1-perfluoro-iso-butyl-3,5-cyclopentylene ethylene),poly(1-perfluoro-tert-butyl-3,5-cyclopentylene ethylene),poly(1-methyl-2-perfluoro-iso-butyl-3,5-cyclopentylene ethylene),poly(1-butyl-2-perfluoro-iso-butyl-3,5-cyclopentylene ethylene),poly(1,2-difluoro-1-trifluoromethyl-2-perfluoroethyl-3,5-cyclopentyleneethylene),poly(1-(1-trifluoromethyl-2,2,3,3,4,4,5,5-octafluorocyclopentyl)-3,5-cyclopentyleneethylene), poly((1,1,2-trifluoro-2-perfluorobutyl)-3,5-cyclopentyleneethylene),poly(1,2-difluoro-1-trifluoromethyl-2-perfluorobutyl-3,5-cyclopentyleneethylene),poly(1-fluoro-1-perfluoroethyl-2,2-bis(trifluoromethyl)-3,5-cyclopentyleneethylene),poly(1,2-difluoro-1-perfluoropropanyl-2-trifluoromethyl-3,5-cyclopentyleneethylene), poly(1-perfluorohexyl-3,5-cyclopentylene ethylene),poly(1-methyl-2-perfluorohexyl-3,5-cyclopentylene ethylene),poly(1-butyl-2-perfluorohexyl-3,5-cyclopentylene ethylene),poly(1-hexyl-2-perfluorohexyl-3,5-cyclopentylene ethylene),poly(1-octyl-2-perfluorohexyl-3,5-cyclopentylene ethylene),poly(1-perfluoroheptyl-3,5-cyclopentylene ethylene),poly(1-perfluorooctyl-3,5-cyclopentylene ethylene),poly(1-perfluorodecanyl-3,5-cyclopentylene ethylene),poly(1,1,2-trifluoro-perfluoropentyl-3,5-cyclopentylene ethylene),poly(1,2-difluoro-1-trifluoromethyl-2-perfluorobutyl-3,5-cyclopentyleneethylene), poly(1,1,2-trifluoro-perfluorohexyl-3,5-cyclopentyleneethylene),poly(1,2-difluoro-1-trifluoromethyl-2-perfluoropentyl-3,5-cyclopentyleneethylene), poly(1,2-bis(perfluorobutyl)-3,5-cyclopentylene ethylene),poly(1,2-bis(perfluorohexyl)-3,5-cyclopentylene ethylene),poly(1-methoxy-2-trifluoromethyl-3,5-cyclopentylene ethylene),poly(1-tert-butoxymethyl-2-trifluoromethyl-3,5-cyclopentylene ethylene),and poly(1,1,3,3,3a,6a-hexafluorofuranyl-3,5-cyclopentylene ethylene).

Furthermore, in the present invention, specific examples of thefluorine-containing cyclic olefin polymer (A) containing the repeatingstructural unit represented by the general formula (1) includepoly(1-fluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene),poly(1-fluoro-1-trifluoromethyl-3,5-cyclopentylene ethylene),poly(1-methyl-1-fluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene),poly(1,1-difluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene),poly(1,2-difluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene),poly(1-perfluoroethyl-3,5-cyclopentylene ethylene),poly(1,1-bis(trifluoromethyl)-3,5-cyclopentylene ethylene),poly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene),poly(1,2-bis(trifluoromethyl)-3,5-cyclopentylene ethylene),poly(1-perfluoropropyl-3,5-cyclopentylene ethylene),poly(1-methyl-2-perfluoropropyl-3,5-cyclopentylene ethylene),poly(1-butyl-2-perfluoropropyl-3,5-cyclopentylene ethylene),poly(1-perfluoro-iso-propyl-3,5-cyclopentylene ethylene),poly(1-methyl-2-perfluoro-iso-propyl-3,5-cyclopentylene ethylene),poly(1,2-difluoro-1,2-bis(trifluoromethyl)-3,5-cyclopentylene ethylene),poly(1,1,2,2,3,3,3a,6a-octafluorocyclopentyl-4,6-cyclopentyleneethylene),poly(1,1,2,2,3,3,4,4,3a,7a-decafluorocyclohexyl-5,7-cyclopentyleneethylene), poly(1-perfluorobutyl-3,5-cyclopentylene ethylene),poly(1-perfluoro-iso-butyl-3,5-cyclopentylene ethylene),poly(1-perfluoro-tert-butyl-3,5-cyclopentylene ethylene),poly(1-methyl-2-perfluoro-iso-butyl-3,5-cyclopentylene ethylene),poly(1-butyl-2-perfluoro-iso-butyl-3,5-cyclopentylene ethylene),poly(1,2-difluoro-1-trifluoromethyl-2-perfluoroethyl-3,5-cyclopentyleneethylene),poly(1-(1-trifluoromethyl-2,2,3,3,4,4,5,5-octafluorocyclopentyl)-3,5-cyclopentyleneethylene), poly((1,1,2-trifluoro-2-perfluorobutyl)-3,5-cyclopentyleneethylene),poly(1,2-difluoro-1-trifluoromethyl-2-perfluorobutyl-3,5-cyclopentyleneethylene),poly(1-fluoro-1-perfluoroethyl-2,2-bis(trifluoromethyl)-3,5-cyclopentyleneethylene),poly(1,2-difluoro-1-perfluoropropanyl-2-trifluoromethyl)-3,5-cyclopentyleneethylene), poly(1-perfluorohexyl-3,5-cyclopentylene ethylene),poly(1-methyl-2-perfluorohexyl-3,5-cyclopentylene ethylene),poly(1-butyl-2-perfluorohexyl-3,5-cyclopentylene ethylene),poly(1-hexyl-2-perfluorohexyl-3,5-cyclopentylene ethylene),poly(1-octyl-2-perfluorohexyl-3,5-cyclopentylene ethylene),poly(1-perfluoroheptyl-3,5-cyclopentylene ethylene),poly(1-perfluorooctyl-3,5-cyclopentylene ethylene),poly(1-perfluorodecanyl-3,5-cyclopentylene ethylene),poly(1,1,2-trifluoro-perfluoropentyl-3,5-cyclopentylene ethylene),poly(1,2-difluoro-1-trifluoromethyl-2-perfluorobutyl-3,5-cyclopentyleneethylene), poly(1,1,2-trifluoro-perfluorohexyl-3,5-cyclopentyleneethylene),poly(1,2-difluoro-1-trifluoromethyl-2-perfluoropentyl-3,5-cyclopentyleneethylene), poly(1,2-bis(perfluorobutyl)-3,5-cyclopentylene ethylene),poly(1,2-bis(perfluorohexyl)-3,5-cyclopentylene ethylene),poly(1-methoxy-2-trifluoromethyl-3,5-cyclopentylene ethylene),poly(1-tert-butoxymethyl-2-trifluoromethyl-3,5-cyclopentylene ethylene),poly(1,1,3,3,3a,6a-hexafluorofuranyl-3,5-cyclopentylene ethylene),poly(1-fluoro-2-trifluoromethoxy-3,5-cyclopentylene ethylene),poly(1-fluoro-1-trifluoromethoxy-3,5-cyclopentylene ethylene),poly(1-methyl-1-fluoro-2-trifluoromethoxy-3,5-cyclopentylene ethylene),poly(1,1-difluoro-2-trifluoromethoxy-3,5-cyclopentylene ethylene),poly(1,2-difluoro-2-trifluoromethoxy-3,5-cyclopentylene ethylene),poly(1-perfluoroethoxy-3,5-cyclopentylene ethylene),poly(1,1-bis(trifluoromethoxy)-3,5-cyclopentylene ethylene),poly(1,1,2-trifluoro-2-trifluoromethoxy-3,5-cyclopentylene ethylene),poly(1,2-bis(trifluoromethoxy)-3,5-cyclopentylene ethylene),poly(1-perfluoropropoxy-3,5-cyclopentylene ethylene),poly(1-methyl-2-perfluoropropoxy-3,5-cyclopentylene ethylene),poly(1-butyl-2-perfluoropropoxy-3,5-cyclopentylene ethylene),poly(1-perfluoro-iso-propoxy-3,5-cyclopentylene ethylene),poly(1-methyl-2-perfluoro-iso-propoxy-3,5-cyclopentylene ethylene),poly(1,2-difluoro-1,2-bis(trifluoromethoxy)-3,5-cyclopentyleneethylene), poly(1-perfluorobutoxy-3,5-cyclopentylene ethylene),poly(1-perfluoro-iso-butoxy-3,5-cyclopentylene ethylene),poly(1-perfluoro-tert-butoxy-3,5-cyclopentylene ethylene),poly(1-methyl-2-perfluoro-iso-butoxy-3,5-cyclopentylene ethylene),poly(1-butyl-2-perfluoro-iso-butoxy-3,5-cyclopentylene ethylene),poly(1,2-difluoro-1-trifluoromethoxy-2-perfluoroethoxy-3,5-cyclopentyleneethylene), poly((1,1,2-trifluoro-2-perfluorobutoxy)-3,5-cyclopentyleneethylene),poly(1,2-difluoro-1-trifluoromethoxy-2-perfluorobutoxy-3,5-cyclopentyleneethylene),poly(1-fluoro-1-perfluoroethoxy-2,2-bis(trifluoromethoxy)-3,5-cyclopentyleneethylene),poly(1,2-difluoro-1-perfluoropropoxy-2-trifluoromethoxy-3,5-cyclopentyleneethylene), poly(1-perfluorohethoxy-3,5-cyclopentylene ethylene),poly(1-methyl-2-perfluorohethoxy-3,5-cyclopentylene ethylene),poly(1-butyl-2-perfluorohethoxy-3,5-cyclopentylene ethylene),poly(1-hexyl-2-perfluorohethoxy-3,5-cyclopentylene ethylene),poly(1-octyl-2-perfluorohethoxy-3,5-cyclopentylene ethylene),poly(1-perfluoroheptoxy-3,5-cyclopentylene ethylene),poly(1-perfluorooctoxy-3,5-cyclopentylene ethylene),poly(1-perfluorodetoxy-3,5-cyclopentylene ethylene),poly(1,1,2-trifluoro-perfluoropentoxy-3,5-cyclopentylene ethylene),poly(1,2-difluoro-1-trifluoromethoxy-2-perfluorobutoxy-3,5-cyclopentyleneethylene), poly(1,1,2-trifluoro-2-perfluorohethoxy-3,5-cyclopentyleneethylene),poly(1,2-difluoro-1-trifluoromethoxy-2-perfluoropentyl-3,5-cyclopentyleneethylene), poly(1,2-bis(perfluorobutoxy)-3,5-cyclopentylene ethylene),poly(1,2-bis(perfluorohethoxy)-3,5-cyclopentylene ethylene),poly(1-methoxy-2-trifluoromethoxy-3,5-cyclopentylene ethylene),poly(1-tert-butoxymethyl-2-trifluoromethoxy-3,5-cyclopentyleneethylene), poly(1-(2′,2′,2′,-trifluoroethoxy)-3,5-cyclopentyleneethylene), poly(1-(2′,2′,3′,3′,3′-pentafluoropropoxy)-3,5-cyclopentyleneethylene),poly(1-methyl-2-(2′,2′,3′,3′,3′-pentafluoropropoxy)-3,5-cyclopentyleneethylene),poly(1-butyl-2-(2′,2′,3′,3′,3′-pentafluoropropoxy)-3,5-cyclopentyleneethylene), poly(1-(1′,1′,1′-trifluoro-iso-propoxy)-3,5-cyclopentyleneethylene),poly(1-methyl-(1′,1′,1′-trifluoro-iso-propoxy)-3,5-cyclopentyleneethylene),poly(1-(2′,2′,3′,3′,4′,4′,4′-heptafluorobutoxy)-3,5-cyclopentyleneethylene), poly(1-(1′,1′,1′-trifluoro-iso-butoxy)-3,5-cyclopentyleneethylene), poly(1-(1′,1′,1′-trifluoro-iso-butoxy)-3,5-cyclopentyleneethylene),poly(1-methyl-2-(1′,1′,1′-trifluoro-iso-butoxy)-3,5-cyclopentyleneethylene),poly(1-butyl-2-(1′,1′,1′-trifluoro-iso-butoxy)-3,5-cyclopentyleneethylene),poly(1,2-difluoro-1-trifluoromethoxy-2-(2′,2′,2′-trifluoroethoxy)-3,5-cyclopentyleneethylene),poly(1,1,2-trifluoro-2-(2′,2′,3′,3′,4′,4′,4′-heptafluorobutoxy)-3,5-cyclopentyleneethylene),poly(1,2-difluoro-1-trifluoromethoxy-2-(2′,2′,3′,3′,4′,4′,4′-heptafluorobutoxy)-3,5-cyclopentyleneethylene),poly(1-fluoro-1-(2′,2′,2′,-trifluoroethoxy)-2,2-bis(trifluorometboxy)-3,5-cyclopentyleneethylene),poly(1,2-difluoro-1-(2′,2′,3′,3′,3′-pentafluoropropoxy)-2-trifluoromethoxy-3,5-cyclopentyleneethylene),poly(1-(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,6′-undecafluorohethoxy)-3,5-cyclopentyleneethylene),poly(1-methyl-2-(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,6′-undecafluorohethoxy)-3,5-cyclopentyleneethylene),poly(1-butyl-2-(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,6′-undecafluorohethoxy)-3,5-cyclopentyleneethylene),poly(1-hexyl-2-(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,6′-undecafluorohethoxy)-3,5-cyclopentyleneethylene),poly(1-octyl-2-(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,6′-undecafluorohethoxy)-3,5-cyclopentyleneethylene),poly(1-(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,7′,7′,7′-tridecafluoroheptoxy)-3,5-cyclopentyleneethylene),poly(1-(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,7′,7′,8′,8′,8′-pentadecafluorooctoxy)-3,5-cyclopentyleneethylene),poly(1-(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,7′,7′,8′,8′,9′,9′,9′-heptadecafluorodecoxy)-3,5-cyclopentyleneethylene),poly(1,1,2-trifluoro-2-(1′,1′,1′-trifluoro-iso-propoxy)-3,5-cyclopentyleneethylene),poly(1,2-difluoro-1-trifluoromethoxy-2-(2′,2′,3′,3′,4′,4′,4′-heptafluorobutoxy)-3,5-cyclopentyleneethylene),poly(1,1,2-trifluoro-(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,6′-undecafluorohethoxy)-3,5-cyclopentyleneethylene),poly(1,2-bis(2′,2′,3′,3′,4′,4′,4′-heptafluorobutoxy)-3,5-cyclopentyleneethylene),poly(1,2-bis(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,6′-undecafluorohethoxy)-3,5-cyclopentyleneethylene), and the like.

Furthermore, in the present invention, the fluorine-containing cyclicolefin copolymer having the repeating structural unit [I] represented bythe general formula (1) and the repeating structural unit [II]represented by the following general formula (2) has a molar ratio ofthe structural unit [I] to the structural unit [II] of [I]/[II]=95/5 to25/75 and a fluorine atom content rate of 40 to 75% by mass. Further,the structural unit [I] does not contain the repeating structural unitrepresented by the general formula (2).

With such a constitution, the heat resistance of a film is improvedwhile a good releasing property is maintained, and therefore, an imprintproduct solving a problem of scratching on the film surface can beobtained. With the glass transition temperature which is an index of theheat resistance of the film, by introducing a rigid aliphatic ringstructure of the structural unit [II] represented by the general formula(2), the mobility of the polymer decreases under heating, as comparedwith the structural unit [I] represented by the general formula (1), andthus, the glass transition temperature increases without interferingwith the characteristics of the fluorine-containing polymer and the heatresistance of the film can be improved.

Further, in the following description, unless otherwise specified, thefluorine-containing cyclic olefin polymer (A) may include afluorine-containing cyclic olefin copolymer.

Furthermore, a fluorine-containing cyclic olefin copolymer having therepeating structural unit [I] represented by the general formula (1) andthe repeating structural unit [II] represented by the following generalformula (2) can solve the problem of the scratching of the film surfaceby introducing a rigid ring structure of the repeating structural unit[II] to improve the surface hardness such as a pencil hardness. If[I]/[II] is less than 95/5, the effect of improving the heat resistanceand the effect of solving the problem of the scratch on the film surfaceare low, and the molar ratio is preferably [I]/[II]=90/10 to 25/75.

In the formula (2), at least one of R⁵ to R⁸ is fluorine,fluorine-containing alkyl having 1 to 10 carbon atoms,fluorine-containing alkoxy having 1 to 10 carbon atoms, orfluorine-containing alkoxyalkyl having 2 to 10 carbon atoms. In the casewhere R⁵ to R⁸ are fluorine-free groups, R⁵ to R⁸ are selected fromhydrogen, alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10carbon atoms, and alkoxyalkyl having 2 to 10 carbon atoms. R⁵ to R⁸ maybe the same as or different from each other. R⁵ to R⁸ may be combinedwith one another to form a ring structure. n represents an integer of 1or 2.

In the present invention, with the fluorine-containing cyclic olefinpolymer, R¹ to R⁴ of the repeating structural unit represented by thegeneral formula (1) and R⁵ to R⁸ of the repeating structural unitrepresented by the general formula (2) may be the same as or differentfrom each other, and the fluorine-containing cyclic olefin polymer maybe one including a combination of two or more structural units, in whichR¹ to R⁴ or R⁵ to R⁸ are different from one another.

In the present invention, specific examples of the fluorine-containingcyclic olefin copolymer containing the repeating structural unitrepresented by the general formula (2) includepoly(3-fluoro-4-trifluoromethyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-fluoro-3-trifluoromethyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-methyl-3-fluoro-4-trifluoromethyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,3-difluoro-4-trifluoromethyl-7,9-tricyclo[4.3.0.1^(2,5)]decanylene ethylene),poly(3,4-difluoro-4-trifluoromethyl-7,9-tricyclo[4.3.0.1^(2,5)]decanylene ethylene),poly(3-perfluoroethyl-7,9-tricyclo[4.3.0.1^(2,5)]decanylene ethylene),poly(3,3-bis(trifluoramethyl)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,3,4-trifluoro-4-trifluoromethyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,4-bistrifluoromethyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene), poly(3-perfluoropropyl-7,9-tricyclo[4.3.0.1⁴⁵]decanyleneethylene),poly(3-methyl-4-perfluoropropyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-butyl-4-perfluoropropyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-perfluoro-iso-propyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-methyl-9-perfluoro-iso-propyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,4-difluoro-3,4-bis(trifluoromethyl)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(2,3,3,4,4,5,5,6-octafluoro-9,11-tetracyclo[5.5.1.0^(2,6).0^(8,12)]tridecanyleneethylene),poly(2,3,3,4,4,5,5,6,6,7-decafluoro-10,12-tetracyclo[6.5.1.0^(2,7).0^(9,13)]tetradecanyleneethylene), poly(3-perfluorobutyl-7,9-tricyclo[4.3.0.1²⁻⁵]decanyleneethylene),poly(3-perfluoro-iso-butyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-perfluoro-tert-butyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-methyl-4-perfluoro-tert-butyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-butyl-4-perfluoro-tert-butyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,4-dimethyl-3-perfluoro-tert-butyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,3,4-trifluoro-4-perfluorobutyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,4-difluoro-3-trifluoromethyl-4-perfluorobutyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-fluoro-3-perfluoroethyl-4,4-bis(trifluoromethyl)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,4-difluoro-3-perfluoropropanyl-4-trifluoromethyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene), poly(3-perfluorohexyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-methyl-4-perfluorohexyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-butyl-4-perfluorohexyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-hexyl-4-perfluorohexyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-octyl-4-perfluorohexyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene), poly(3-perfluoroheptyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene), poly(3-perfluorodecanyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,3,4-trifluoro-4-perfluoropentyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,4-difluoro-3-trifluoromethyl-4-perfluorobutyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,3,4-trifluoro-3-perfluorohexyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,4-difluoro-3-trifluoromethyl-4-perfluoropentyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,4-bis(perfluorobutyl)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,4-bis(perfluorohexyl)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-methoxy-4-trifluoromethyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-tert-butoxymethyl-4-trifluoromethyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(4-fluoro-5-trifluoromethyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-methyl-5-fluoro-5-trifluoromethyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,4-difluoro-5-trifluoromethyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-perfluoroethyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,4-bis(trifluoromethyl)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,4,5-trifluoro-5-trifluoromethyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,5-bis(trifluoromethyl)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-perfluoropropyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,16)]pentadecanyleneethylene),poly(4-methyl-5-perfluoropropyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-methyl-5-perfluoropropyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-butyl-5-perfluoropropyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-perfluoro-iso-propyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-methyl-5-perfluoro-iso-propyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,5-difluoro-4,5-bis(trifluoromethyl)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(3,4,4,5,5,6,6,7-octafluoro-12,14-hexacyclo[7.7.0.1^(2,8).1^(10,16).0^(3,7).0^(11,15)]octadecanyleneethylene),poly(3,4,4,5,5,6,6,7,7,8-decafluoro-13,15-hexacyclo[8.7.0.1^(2,9).1^(11,17).0^(3,8).0^(12,16)]nonadecanyleneethylene),poly(4-perfluorobutyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-perfluoro-iso-butyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-methyl-5-tert-butyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-butyl-5-tert-butyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,5-methyl-4-tert-butyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,4,5-trifluoro-6-perfluorobutyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,6-difluoro-4-trifluoromethyl-5-perfluorobutyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-fluoro-4-perfluoroethyl-5,5-bis(trifluoromethyl)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,5-difluoro-4-perfluoropropanyl-5-trifluoromethyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-perfluorohexyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-methyl-5-perfluorohexyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-butyl-5-perfluorohexyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-hexyl-5-perfluorohexyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-octyl-5-perfluorohexyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-perfluoroheptyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-perfluorooctyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-perfluorodecanyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,4,5-trifluoro-6-perfluoropentyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,5-difluoro-4-trifluoromethyl-6-perfluorobutyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,4,5-trifluoro-12-perfluorohexyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,5-difluoro-4-trifluoromethyl-5-perfluoropentyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,4,5-tris(trifluoromethyl)-5-perfluoro-tert-butyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,5-bis(perfluorohexyl)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-methoxy-5-trifluoromethyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,3).1^(3,6)]pentadecanyleneethylene),poly(3-fluoro-4-trifluoromethoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-fluoro-4-trifluoromethoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-methyl-3-fluoro-4-trifluoromethoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,3-difluoro-4-trifluoromethoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,4-difluoro-4-trifluoromethoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene), poly(3-perfluoroethoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,3,4-trifluoro-4-trifluoromethoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,4-bis(trifluoromethoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene), poly(3-perfluoropropoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-methyl-4-perfluoropropoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-butyl-4-perfluoropropoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-perfluoro-iso-propoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-methyl-4-perfluoro-iso-propoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,4-difluoro-3,4-bis(trifluoromethoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene), poly(3-perfluorobutoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-perfluoro-iso-butoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene), poly(3-perfluoro-tert-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-methyl-4-perfluoro-iso-butoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-butyl-4-perfluoro-iso-butoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,4-difluoro-3-trifluoromethoxy-4-perfluoroethoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly((3,3,4-trifluoro-4-perfluorobutoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,4-difluoro-3-trifluoromethoxy-4-perfluorobutoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-fluoro-3-perfluoroethoxy-2,2-bis(trifluoromethoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,4-difluoro-3-perfluoropropoxy-4-trifluoromethoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene), poly(3-perfluorohethoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-methyl-4-perfluorohethoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-butyl-4-perfluorohethoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-hexyl-4-perfluorohethoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-octyl-4-perfluorohethoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene), poly(3-perfluoroheptoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene), poly(3-perfluorooctoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene), poly(3-perfluorodecoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,3,4-trifluoro-perfluoropentoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,4-difluoro-3-trifluoromethoxy-4-perfluorobutoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,3,4-trifluoro-4-perfluorohethoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,4-difluoro-3-trifluoromethoxy-4-perfluoropentyl-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,4-bis(perfluorobutoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,4-bis(perfluorohethoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-methoxy-4-trifluoromethoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-tert-butoxymethyl-4-trifluoromethoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-(2′,2′,2′,-trifluoroethoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-(2′,2′,3′,3′,3′-pentafluoropropoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-methyl-4-(2′,2′,3′,3′,3′-pentafluoropropoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-butyl-4-(2′,2′,3′,3′,3′-pentafluoropropoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-(1′,1′,1′-trifluoro-iso-propoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-methyl-(1′,1′,1′-trifluoro-iso-propoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-(2′,2′,3′,3′,4′,4′,4′-heptafluorobutoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-(1′,1′,1′-trifluoro-iso-butoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-(1′,1′,1′-trifluoro-iso-butoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-methyl-4-(1′,1′,1′-trifluoro-iso-butoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-butyl-4-(1′,1′,1′-trifluoro-iso-butoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,4-difluoro-3-trifluoromethoxy-4-(2′,2′,2′-trifluoroethoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,3,4-trifluoro-4-(2′,2′,3′,3′,4′,4′,4′-heptafluorobutoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,4-difluoro-3-trifluoromethoxy-4-(2′,2′,3′,3′,4′,4′,4′-heptafluorobutoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-fluoro-3-(2′,2′,2′,-trifluoroethoxy)-4,4-bis(trifluoromethoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,4-difluoro-3-(2′,2′,3′,3′,3′-pentafluoropropoxy)-4-trifluoromethoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,6′-undecafluorohethoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-methyl-4-(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,6′-undecafluorohethoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-butyl-4-(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,6′-undecafluorohethoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-hexyl-4-(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,6′-undecafluorohethoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-octyl-4-(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,6′-undecafluorohethoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,7′,7′,7′-tridecafluoroheptoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,7′,7′,8′,8′,8′-pentadecafluorooctoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3-(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,7′,7′,8′,8′,9′,9′,9′-heptadecafluorodecoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,3,4-trifluoro-4-(1′,1′,1′-trifluoro-iso-propoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,4-difluoro-3-trifluoromethoxy-4-(2′,2′,3′,3′,4′,4′,4′-heptafluorobutoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,3,4-trifluoro-(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,6′-undecafluorohethoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,4-bis(2′,2′,3′,3′,4′,4′,4′-heptafluorobutoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(3,4-bis(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,6′-undecafluorohethoxy)-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(4-fluoro-5-trifluoromethoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-fluoro-5-trifluoromethoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-methyl-4-fluoro-5-trifluoromethoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,4-difluoro-5-trifluoromethoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,5-difluoro-5-trifluoromethoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene), poly(4-perfluoroethoxy-7,9-tricyclo[4.3.0.1^(2,5)]decanyleneethylene),poly(4,4,5-trifluoro-5-trifluoromethoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,5-bis(trifluoromethoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-perfluoropropoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-methyl-5-perfluoropropoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-butyl-5-perfluoropropoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-perfluoro-iso-propoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-methyl-5-perfluoro-iso-propoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,5-difluoro-4,5-bis(trifluoromethoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-perfluorobutoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-perfluoro-iso-butoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-perfluoro-tert-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-methyl-5-perfluoro-iso-butoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-butyl-5-perfluoro-iso-butoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,5-difluoro-4-trifluoromethoxy-5-perfluoroethoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly((4,4,5-trifluoro-5-perfluorobutoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,5-difluoro-4-trifluoromethoxy-5-perfluorobutoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-fluoro-4-perfluoroethoxy-5,5-bis(trifluoromethoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,5-difluoro-4-perfluoropropoxy-5-trifluoromethoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-perfluorohethoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-methyl-5-perfluorohethoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-butyl-5-perfluorohethoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-hexyl-5-perfluorohethoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-octyl-5-perfluorohethoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-perfluoroheptoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-perfluorooctoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-perfluorodecoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,4,5-trifluoroperfluoro-pentoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,5-difluoro-4-trifluoromethoxy-5-perfluorobutoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,4,5-trifluoro-5-perfluorohethoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,5-difluoro-4-trifluoromethoxy-5-perfluoropentyl-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,5-bis(perfluorobutoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanylene ethylene),poly(4,5-bis(perfluorohethoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-methoxy-5-trifluoromethoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene), poly(4-tert-butoxymethyl5-trifluoromethoxy-10,12-pentacyclo[6.5.1.0^(2,7).0⁹¹³.1^(3,6)]pentadecanylene ethylene),poly(4-(2′,2′,2′,-trifluoroethoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-(2′,2′,3′,3′,3′-pentafluoropropoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-methyl-5-(2′,2′,3′,3′,3′-pentafluoropropoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-butyl-5-(2′,2′,3′,3′,3′-pentafluoropropoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-(1′,1′,1′-trifluoro-iso-propoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-methyl-(1′,1′,1′-trifluoro-iso-propoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-(2′,2′,3′,3′,4′,4′,4′-heptafluorobutoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-(1′,1′,1′-trifluoro-iso-butoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-(1′,1′,1′-trifluoro-iso-butoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-methyl-5-(1′,1′,1′-trifluoro-iso-butoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-butyl-5-(1′,1′,1′-trifluoro-iso-butoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).]pentadecanyleneethylene),poly(4,5-difluoro-4-trifluoromethoxy-5-(2′,2′,2′-trifluoroethoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,4,5-trifluoro-5-(2′,2′,3′,3′,4′,4′,4′-heptafluorobutoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,5-difluoro-4-trifluoromothoxy-4-(2′,2′,3′,3′,4′,4′,4′-heptafluorobutoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-fluoro-4-(2′,2′,2′,-trifluoroethoxy)-5,5-bis(trifluoromethoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,5-difluoro-4-(2′,2′,3′,3′,3′-pentafluoropropoxy)-5-trifluoromethoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,6′-undecafluorohethoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-methyl-5-(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,6′-undecafluorohethoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-butyl-5-(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,6′-undecafluorohethoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-hexyl-5-(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,6′-undecafluorohethoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-octyl-5-(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,6′-undecafluorohethoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,7′,7′,7′-tridecafluoroheptoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,7′,7′,8′,8′,8′-pentadecafluorooctoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4-(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,7′,7′,8′,8′,9′,9′,9′-heptadecafluorodecoxy-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,4,5-trifluoro-5-(1′,1′,1′-trifluoro-iso-propoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,5-difluoro-4-trifluoromethoxy-5-(2′,2′,3′,3′,4′,4′,4′-heptafluorobutoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,4,5-trifluoro-(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,6′-undecafluorohethoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1⁶]pentadecanylene ethylene),poly(4,5-bis(2′,2′,3′,3′,4′,4′,4′-heptafluorobutoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene),poly(4,5-bis(2′,2′,3′,3′,4′,4′,5′,5′,6′,6′,6′-undecafluorohethoxy)-10,12-pentacyclo[6.5.1.0^(2,7).0^(9,13).1^(3,6)]pentadecanyleneethylene), and the like.

Furthermore, within a range which does not impair the effect of thepresent invention, in addition to the repeating structural unitsrepresented by the general formulae (1) and (2), other repeatingstructural units may be contained with a fluorine atom content rate inthe range from 40 to 75% by mass, but the repeating structural unit ofthe general formula (1) or the general formula (1) or (2) is usuallyfrom 30 to 100% by mass, preferably from 70 to 100% by mass, and morepreferably from 90 to 100% by mass.

Furthermore, in the present invention, the fluorine-containing cyclicolefin polymer (A) containing the repeating structural unit representedby the general formula (1) preferably has a storage modulus or lossmodulus by the measurement of a dynamic mechanical analysis by tensilemode (a frequency of 1 Hz and a temperature increase rate of 3°C./minute) having a variable region in the range from −1 to 0 MPa/° C.with respect to a temperature varying in the temperature region of theglass transition temperature or higher. The characteristics are inducedfrom formation of hydrogen bonds between the polymers or in the moleculeof the polymer by incorporating the main chain of the repeatingstructural unit with a hydrocarbon structure and by incorporating theside chain of the repeating structural unit with a substituent selectedfrom fluorine, fluorine-containing alkyl, fluorine-containing alkoxyhaving 1 to 10 carbon atoms, and fluorine-containing alkoxyalkyl having2 to 10 carbon atoms, as at least one of R¹ to R⁴, not fromcrystallinity or crosslink due to chemical bonds. By the hydrogen bondsgenerated by such a specific structure, the change in the storagemodulus or loss modulus with respect to the change in the temperature inthe temperature region of the glass transition temperature or higher hasa flat region ranging from −1 to 0 MPa/° C., preferably from −0.5 to 0MPa/° C., and more preferably from −0.2 to 0 MPa/° C.

Moreover, in the present invention, the fluorine-containing cyclicolefin copolymer containing the repeating structural unit [I]represented by the general formula (1) and the repeating structural unit[II] represented by the general formula (2) has a molar ratio of thestructural unit [I] to the structural unit [II] of [I]/[II]=95/5 to25/75. Further, the structural unit [I] does not contain the repeatingstructural unit represented by the general formula (2).

As described above, the change in the storage modulus or loss modulushas a flat region, which is induced from formation of hydrogen bondsbetween the polymers or in the molecule of the polymer by incorporatingthe main chain of the repeating structural unit with a hydrocarbonstructure or by incorporating the side chain of the repeating structuralunit with a substituent selected from fluorine, fluorine-containingalkyl, fluorine-containing alkoxy having 1 to 10 carbon atoms, andfluorine-containing alkoxyalkyl having 2 to 10 carbon atoms, as at leastone of R¹ to R⁴ and R⁵ to R⁸. By the hydrogen bonds generated by such aspecific structure, the change in the storage modulus or loss moduluswith respect to the change in the temperature in the temperature regionof the glass transition temperature or higher has a flat region rangingfrom −1 to 0 MPa/° C. If the molar ratio is more than 25/75, the flatvariable region of the storage modulus or the loss modulus is lost, andthus, the effect due to the hydrogen bond is not exhibited.

The fluorine-containing cyclic olefin polymer and thefluorine-containing cyclic olefin copolymer of the present invention areamorphous transparent polymers.

Generally, in the case where the amorphous thermoplastic polymer doesnot have such a hydrogen bond or chemical crosslinking present therein,it shows a drastically lowered modulus in the temperature region of theglass transition temperature or higher, and a change in the storagemodulus or loss modulus with respect to the change in the temperature ofat least −10 MPa/° C. or less. On the other hand, the above-describedcharacteristics of the fluorine-containing cyclic olefin polymer (A) ofthe present invention are derived from reversible interactions betweenthe physical hydrogen bonds with respect to the change in thetemperature.

Moreover, in the present invention, the fluorine-containing cyclicolefin polymer containing the repeating structural unit represented bythe general formula (1), or the fluorine-containing cyclic olefincopolymer containing the repeating structural units represented by thegeneral formulae (1) and (2) preferably has the above-described flatvariable region of the storage modulus or the loss modulus in a regionof the storage modulus or the loss modulus of 0.1 MPa or more, morepreferably 0.1 to 10000 MPa, and even more preferably 0.1 to 1000 MPa,in the temperature region of the glass transition temperature or higher,in the measurement of a dynamic mechanical analysis by tensile mode(frequency 1 Hz, temperature increase rate of 3° C./minute). With 0.1MPa or more, the shape of an imprint product can be maintained, theshrinkage change during cooling is small, and the dimensional precisionof the transcription improves in the heating and cooling processes inthe step of production of the imprint product.

In this regard, the change in the modulus and shrinkage rate in theheating and cooling processes in the step of production of thenanoimprint film by solution-coating, heating, and drying, or heatingand pressing is inhibited to a minimal degree and optimized, and as aresult, an imprint product having a fine pattern transcribed over itssurface with high dimensional precision can be formed. Further,incorporation of fluorine makes it possible to produce a film having asmall surface tension and an excellent releasing property from a mold.Particularly, a nanoimprint method by solution-coating, heating, anddrying is suitable for production of an imprint product having a highdegree of freedom of the film thickness and a large area.

In the present invention, the glass transition temperature is a maximumvalue of the loss modulus/the storage modulus (=tan δ) obtained bymeasuring the dynamic mechanical change with a constant rise or fall ofthe temperature of a sample, or it includes a change point obtained byendothermic or exothermic measurement by means of differential scanningcalorimetry, and the like.

The glass transition temperature is usually in the range from 30 to 250°C., preferably from 50 to 200° C., and more preferably from 60 to 160°C. If the glass transition temperature is 30° C. or higher, it is easyto maintain the imprint product shape with high precision, that is apattern shape molded after releasing, whereas if the glass transitiontemperature is 250° C. or lower, the heating treatment temperature canbe lowered to perform melt-fluidizing, and thus, yellowing ordeterioration of a support does not easily occur.

In the present invention, the fluorine atom content rate in thefluorine-containing cyclic olefin polymer containing the repeatingstructural unit represented by the general formula (1), and, thefluorine-containing cyclic olefin copolymer containing the repeatingstructural units represented by the general formulae (1) and (2) can bedetermined by the following equation (1).Content rate of fluorine atoms (% by mass)=(Fn×19)×100/Fw  (1)

In equation (1), Fn represents the number of fluorine atoms inconsideration of its molar proportion in the structural unit representedby the general formula (1) and the repeating structural unit representedby the general formula (2), Fw represents a formula weight inconsideration of its molar proportion in the repeating structural unitrepresented by the general formula (1) and the repeating structural unitrepresented by the general formula (2), and the fluorine atom contentrate is 40 to 75% by mass, and preferably 42 to 68% by mass. If thefluorine atom content rate is less than 40% by mass, the flat variableregion of the storage modulus or the loss modulus is small or not shown,and the effect due to the hydrogen bonds is not exerted, whereas if thefluorine atom content rate is more than 75% by mass, the number ofhydrogen atoms in the structural unit is small, and similarly, theeffect due to the hydrogen bonds is not exerted.

In the present invention, the fluorine-containing cyclic olefin polymeror fluorine-containing cyclic olefin copolymer has a weight averagemolecular weight (Mw) in terms of polystyrene, as measured by means ofgel permeation chromatography (GPC), with a sample concentration of 3.0to 9.0 mg/ml of usually 5,000 to 1,000,000, and preferably 10,000 to300,000. If this weight average molecular weight (Mw) is 5,000 or more,it is possible to exert physical properties having a region in which thechange of the storage modulus or loss modulus with respect to the changein the temperature is from −1 to 0 MPa/° C.

In addition, if this weight average molecular weight (Mw) is 1,000,000or less, the solvent solubility or the fluidity during heating andpressing molding is good. Further, the ratio of the weight averagemolecular weight (Mw) to the average molecular weight (Mn), that is, themolecular weight distribution (Mw/Mn) is usually in the range from 1.0to 5.0.

For example, in order to form a coating film having uniform thicknessand obtain a good heating molding property, a wide molecular weightdistribution is preferred, and it is more preferably from 1.4 to 5.0, orfrom 1.5 to 3.0.

In the fluorine-containing cyclic olefin polymer (A) of the presentinvention, by incorporating specific structures represented by thegeneral formula (1) and the general formula (2), an extremely lowrefractive index with respect to D-rays can be obtained.

The refractive index with respect to light having a wavelength of D-raysis usually from 1.48 or less, and preferably from 1.30 to 1.48, and inthis range of the refractive index, light shows superior linearity. Forthis reason, the light transmittance in the visible light region ispreferably 80% or more, and more preferably from 85 to 100%.

Furthermore, the fluorine-containing cyclic olefin polymer or thefluorine-containing cyclic olefin copolymer of the present invention hasa mass decrease ratio of usually less than 0.1%, and preferably lessthan 0.07% when heated at 300° C. for 5 minutes, and itsthermoplasticity and thermal stability are excellent, thus making itpossible to heating and pressing molding.

In the present invention, the fluorine-containing cyclic olefin polymer(A) can be synthesized by polymerizing the fluorine-containing cyclicolefin monomer represented by the general formula (3) with aring-opening metathesis polymerization catalyst, and hydrogenating anolefin portion in the main chain of the resulting polymer.

In the formula (3), at least one of R¹ to R⁴ is fluorine,fluorine-containing alkyl having 1 to 10 carbon atoms,fluorine-containing alkoxy having 1 to 10 carbon atoms, orfluorine-containing alkoxyalkyl having 2 to 10 carbon atoms. In the casewhere R¹ to R⁴ are fluorine-free groups, R¹ to R⁴ are selected fromhydrogen, alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10carbon atoms, and alkoxyalkyl having 2 to 10 carbon atoms. R¹ to R⁴ maybe the same as or different from each other. R¹ to R⁴ may be combinedwith one another to form a ring structure.

More specifically, in the general formula (3), examples of R¹ to R⁴include fluorine; or alkyl having 1 to 10 carbon atoms, in which a partor all of hydrogen atoms of the alkyl group is (are) substituted withfluorine atom(s), such as fluoromethyl, difluoromethyl, trifluoromethyl,trifluoroethyl, pentafluoroethyl, heptafluoropropyl,hexafluoroisopropyl, heptafluoroisopropyl, hexafluoro-2-methylisopropyl,perfluoro-2-methylisopropyl, n-perfluorobutyl, n-perfluoropentyl,perfluorocyclopentyl; alkoxy having 1 to 10 carbon atoms in which a partor all of hydrogen atoms of the alkoxy group is (are) substituted withfluorine atom(s), such as fluoromethoxy, difluoromethoxy,trifluoromethoxy, trifluoroethoxy, pentafluoroethoxy,heptafluoropropoxy, hexafluoroisopropoxy, heptafluoroisopropoxy,hexafluoro-2-methylisopropoxy, perfluoro-2-methylisopropoxy,n-perfluorobutoxy, n-perfluoropentoxy, perfluorocyclopentoxy; andalkoxyalkyl having 2 to 10 carbon atoms in which a part or all ofhydrogen atoms of the alkoxy group is (are) substituted with fluorineatom(s), such as fluoromethoxymethyl, difluoromethoxymethyl,trifluoromethoxymethyl, trifluoroethoxymethyl, pentafluoroethoxymethyl,heptafluoropropoxymethyl, hexafluoroisopropoxymethyl,heptafluoroisopropoxymethyl, hexafluoro-2-methylisopropoxymethyl,perfluoro-2-methylisopropoxymethyl, n-perfluorobutoxymethyl,n-perfluoropentoxymethyl, perfluorocyclopentoxymethyl, and the like.

Furthermore, R¹ to R⁴ may be combined with one another to form a ringstructure or to form a ring such as perfluorocycloalkyl,perfluorocycloether, which is formed through oxygen.

Furthermore, examples of other R¹ to R⁴ containing no fluorine includehydrogen, or alkyl having 1 to 10 carbon atoms, for example, alkyl suchas methyl, ethyl, propyl, isopropyl, 2-methylisopropyl, n-butyl,n-pentyl, cyclopentyl; alkoxy having 1 to 10 carbon atoms, such asmethoxy, ethoxy, propoxy, butoxy, pentoxy; and alkoxyalkyl having 2 to10 carbon atoms, such as methoxymethyl, ethoxymethyl, propoxymethyl,butoxymethyl, pentoxymethyl.

Moreover, in the present invention, the monomer used for the productionof the fluorine-containing cyclic olefin polymer (A) may be afluorine-containing cyclic olefin monomer represented by the generalformula (3) individually or a combination of two or more structuralunits, in which at least one of R¹ to R⁴ of the general formula (1) isdifferent from the others.

Furthermore, in the present invention, the monomer used for theproduction of the fluorine-containing cyclic olefin copolymer may becopolymerized with the fluorine-containing cyclic olefin comonomerrepresented by the general formula (4).

In the formula (4), at least one of R⁵ to R⁸ is fluorine,fluorine-containing alkyl having 1 to 10 carbon atoms,fluorine-containing alkoxy having 1 to 10 carbon atoms, orfluorine-containing alkoxyalkyl having 2 to 10 carbon atoms. In the casewhere R⁵ to R⁸ are fluorine-free groups, R⁵ to R⁸ are selected fromhydrogen, alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10carbon atoms, and alkoxyalkyl having 2 to 10 carbon atoms. R⁵ to R⁸ maybe the same as or different from each other. R⁵ to R⁸ may be combinedwith one another to form a ring structure. n represents an integer of 1or 2.

More specifically, in the general formula (4), examples of R⁵ to R⁸include fluorine; or alkyl having 1 to 10 carbon atoms in which apart orall of hydrogen atoms of the alkyl group is (are) substituted withfluorine atom(s), such as fluoromethyl, difluoromethyl, trifluoromethyl,trifluoroethyl, pentafluoroethyl, heptafluoropropyl,hexafluoroisopropyl, heptafluoroisopropyl, hexafluoro-2-methylisopropyl,perfluoro-2-methylisopropyl, n-perfluorobutyl, n-perfluoropentyl,perfluorocyclopentyl; alkoxy having 1 to 10 carbon atoms in which a partor all of hydrogen atoms of the alkoxy group is (are) substituted withfluorine atom(s), such as fluoromethoxy, difluoromethoxy,trifluoromethoxy, trifluoroethoxy, pentafluoroethoxy,heptafluoropropoxy, hexafluoroisopropoxy, heptafluoroisopropoxy,hexafluoro-2-methylisopropoxy, perfluoro-2-methylisopropoxy,n-perfluorobutoxy, n-perfluoropentoxy, perfluorocyclopentoxy; andalkoxyalkyl having 2 to 10 carbon atoms in which a part or all ofhydrogen atoms of the alkoxy group is (are) substituted with fluorineatom(s), such as fluoromethoxymethyl, difluoromethoxymethyl,trifluoromethoxymethyl, trifluoroethoxymethyl, pentafluoroethoxymethyl,heptafluoropropoxymethyl, hexafluoroisopropoxymethyl,heptafluoroisopropoxymethyl, hexafluoro-2-methylisopropoxymethyl,perfluoro-2-methylisopropoxymethyl, n-perfluorobutoxymethyl,n-perfluoropentoxymethyl, perfluorocyclopentoxymethyl, and the like.

Furthermore, R⁵ to R⁸ may be combined with one another to form a ringstructure or to form a ring such as perfluorocycloalkyl,perfluorocycloether, which is formed through oxygen, and the like.

Furthermore, examples of other R⁵ to R⁸ containing no fluorine includehydrogen, or alkyl having 1 to 10 carbon atoms, for example, alkyl suchas methyl, ethyl, propyl, isopropyl, 2-methylisopropyl, n-butyl,n-pentyl, cyclopentyl, alkoxy having 1 to 10 carbon atoms, such asmethoxy, ethoxy, propoxy, butoxy, pentoxy, and alkoxyalkyl having 2 to10 carbon atoms, such as methoxymethyl, ethoxymethyl, propoxymethyl,butoxymethyl, pentoxymethyl.

Furthermore, in the present invention, the monomer used for theproduction of the fluorine-containing cyclic olefin copolymer may be afluorine-containing cyclic olefin monomer represented by the generalformula (4) individually or a combination of two or more structuralunits, in which at least one of R⁵ to R⁸ is different from the others.

The ring-opening metathesis polymerization catalyst used for thepolymerization of fluorine-containing cyclic olefin monomer is notlimited as long as it can perform ring-opening metathesispolymerization, but examples thereof include tungsten-based alkylidenecatalysts such as W(N-2,6-Pr^(i) ₂C₆H₃)(CHBu^(t))(OBu^(t))₂,W(N-2,6-Pr^(i) ₂C₆H₃)(CHBu^(t))(OCMe₂CF₃)₂, W(N-2,6-Pr^(i)₂C₆H₃)(CHBu^(t))(OCMe(CF₃)₂)₂, W(N-2,6-Pr^(i)₂C₆H₃)(CHBu^(t))(OC(CF₃)₃)₂, W(N-2,6-(Me)₂C₆H₃)(CHBu^(t))(OC(CF₃)₃)₂,W(N-2,6-Pr^(i) ₂C₆H₃)(CHCMe₂Ph)(OBu^(t))₂, W(N-2,6-Pr^(i)₂C₆H₃)(CHCMe₂Ph)(OCMe₂CF₃)₂, W(N-2,6-Pr^(i)₂C₆H₃)(CHCMe₂Ph)(OCMe(CF₃)₂)₂, W(N-2,6-Pr^(i)₂C₆H₃)(CHCMe₂Ph)(OC(CF₃)₃)₂, W(N-2,6-Me₂C₆H₃)(CHCMe₂Ph)(OC(CF₃)₃)₂, orW(N-2,6-Me₂C₆H₃)(CHCHCMePh)(OBu^(t))₂(PR₃),W(N-2,6-Me₂C₆H₃)(CHCHCMe₂)(OBu^(t))₂(PR₃),W(N-2,6-Me₂C₆H₃)(CHCHCPh₂)(OBu^(t))₂(PR₃),W(N-2,6-Me₂C₆H₃)(CHCHCMePh)(OCMe₂(CF₃))₂(PR₃),W(N-2,6-Me₂C₆H₃)(CHCHCMe₂)(OCMe₂(CF₃))₂(PR₃),W(N-2,6-Me₂C₆H₃)(CHCHCPh₂)(OCMe₂(CF₃))₂(PR₃),W(N-2,6-Me₂C₆H₃)(CHCHCMePh)(OCMe(CF₃)₂)₂(PR₃),W(N-2,6-Me₂C₆H₃)(CHCHCMe₂)(OCMe(CF₃)₂)₂(PR₃),W(N-2,6-Me₂C₆H₃)(CHCHCPh₂)(OCMe(CF₃)₂)₂(PR₃),W(N-2,6-Me₂C₆H₃)(CHCHCMePh)(OC(CF₃)₃)₂(PR₃),W(N-2,6-Me₂C₆H₃)(CHCHCMe₂)(OC(CF₃)₃)₂(PR₃),W(N-2,6-Me₂C₆H₃)(CHCHCPh₂)(OC(CF₃)₃)₂(PR₃), W(N-2,6-Pr^(i)₂C₆H₃)(CHCHCMePh)(OCMe₂(CF₃))₂(PR₃), W(N-2,6-Pr^(i)₂C₆H₃)(CHCHCMePh)(OCMe(CF₃)₂)₂(PR₃), W(N-2,6-Pr^(i)₂C₆H₃)(CHCHCMePh)(OC(CF₃)₃)₂(PR₃), W(N-2,6-Pr^(i)₂C₆H₃)(CHCHCMePh)(OPh)₂(PR₃), orW(N-2,6-Me₂C₆H₃)(CHCHCMePh)(OBu^(t))₂(Py),W(N-2,6-Me₂C₆H₃)(CHCHCMe₂)(OBu^(t))₂(Py),W(N-2,6-Me₂C₆H₃)(CHCHCPh₂)(OBu^(t))₂(Py),W(N-2,6-Me₂C₆H₃)(CHCHCMePh)(OCMe₂(CF₃))₂(Py),W(N-2,6-Me₂C₆H₃)(CHCHCMe₂)(OCMe₂(CF₃))₂ (Py),W(N-2,6-Me₂C₆H₃)(CHCHCPh₂)(OCMe₂(CF₃))₂ (Py),W(N-2,6-Me₂C₆H₃)(CHCHCMePh)(OCMe(CF₃)₂)₂ (Py),W(N-2,6-Me₂C₆H₃)(CHCHCMe₂)(OCMe(CF₃)₂)₂ (Py),W(N-2,6-Me₂C₆H₃)(CHCHCPh₂)(OCMe(CF₃)₂)₂(Py),W(N-2,6-Me₂C₆H₃)(CHCHCMePh)(OC(CF₃)₃)₂ (Py),W(N-2,6-Me₂C₆H₃)(CHCHCMe₂)(OC(CF₃)₃)₂ (Py),W(N-2,6-Me₂C₆H₃)(CHCHCPh₂)(OC(CFA₃)₂(Py), W(N-2,6-Pr^(i)₂C₆H₃)(CHCHCMePh)(OCMe₂(CF₃))₂(Py), W(N-2,6-Pr^(i)₂C₆H₃)(CHCHCMePh)(OCMe(CF₃)₂)₂ (Py), W(N-2,6-Pr^(i)₂C₆H₃)(CHCHCMePh)(OC(CF₃)₃)₂(Py), W(N-2,6-Pr^(i)₂C₆H₃)(CHCHCMePh)(OPh)₂(Py);

molybdenum-based alkylidene catalysts such as Mo(N-2,6-Pr^(i)₂C₆H₃)(CHBu^(t))(OBu^(t))_(2,) Mo(N-2,6-Pr^(i)₂C₆H₃)(CHBu^(t))(OCMe₂CF₃)₂, Mo(N-2,6-Pr^(i)₂C₆H₃)(CHBu^(t))(OCMe(CF₃)₂)₂, Mo(N-2,6-Pr^(i)₂C₆H₃)(CHBu^(t))(OC(CF₃)₃)₂, Mo(N-2,6-Me₂C₆H₃)(CHBu^(t))(OC(CF₃)₃)₂,Mo(N-2,6-Pr^(i) ₂C₆H₃)(CHCMe₂Ph)(OCMe₃)₂, Mo(N-2,6-Pr^(i)₂C₆H₃)(CHCMe₂Ph)(OCMe₂(CF₃))₂, Mo(N-2,6-Pr^(i)₂C₆H₃)(CHCMe₂Ph)(OCMe(CF₃)₂)₂, Mo(N-2,6-Pr^(i)₂C₆H₃)(CHCMe₂Ph)(OC(CF₃)₃)₂, Mo(N-2,6-Me₂C₆H₃)(CHCMe₂Ph)(OC(CF₃)₃)₂,Mo(N-2,6-Pr^(i) ₂C₆H₃)(CHCMe₂Ph)(OBu^(t))₂(PR₃), Mo(N-2,6-Pr^(i)₂C₆H₃)(CHCMe₂Ph)(OCMe₂CF₃)₂(PR₃), Mo(N-2,6-Pr^(i)₂C₆H₃)(CHCMe₂Ph)(OCMe(CF₃)₂)₂(PR₃), Mo(N-2,6-Pr^(i)₂C₆H₃)(CHCMe₂Ph)(OC(CF₃)₃)₂(PR₃),Mo(N-2,6-Me₂C₆H₃)(CHCMe₂Ph)(OC(CF₃)₃)₂(PR₃), Mo(N-2,6-Pr^(i)₂C₆H₃)(CHCMe₂Ph)(OBu^(t))₂(Py), Mo(N-2,6-Pr^(i)₂C₆H₃)(CHCMe₂Ph)(OCMe₂CF₃)₂(Py), Mo(N-2,6-Pr^(i)₂C₆H₃)(CHCMe₂Ph)(OCMe(CF₃)₂)₂(Py), Mo(N-2,6-Pr^(i)₂C₆H₃)(CHCMe₂Ph)(OC(CF₃)₃)₂(Py),Mo(N-2,6-Me₂C₆H₃)(CHCMe₂Ph)(OC(CF₃)₃)₂(Py) (wherein Pr^(i) in theformula represents an iso-propyl group, R represents an alkyl group suchas a methyl group, an ethyl group, or an alkoxy group such as a methoxygroup, an ethoxy group, Bu^(t) represents a tert-butyl group, Merepresents a methyl group, Ph represents a phenyl group, and Pyrepresents a pyridine group); and

ruthenium-based alkylidene catalysts such as Ru(CHCHCPh₂)(PPh₃)₂Cl₂(wherein Ph in the formula represents a phenyl group), and the like, andcan be preferably used. In addition, these ring-opening metathesispolymerization catalysts may be used individually or in combination oftwo or more kinds thereof.

On the other hand, in addition to the ring-opening metathesispolymerization catalyst, a ring-opening metathesis polymerizationcatalyst including a combination of an organic transition metal complex,a transition metal halide, or a transition metal oxide with a Lewis acidas a co-catalyst may be used, but it has a low catalyst activity and isundesirable industrially.

In the ring-opening metathesis polymerization of the fluorine-containingcyclic olefin monomer, the molar ratio of the fluorine-containing cyclicolefin monomer to the ring-opening metathesis polymerization catalystis, in the case of a transition metal alkylidene catalyst such astungsten, molybdenum, or ruthenium, and the like, usually 100 to 30,000moles, and preferably 1,000 to 20,000 moles of the monomer, with respectto one mole of the transition metal alkylidene catalyst.

Furthermore, in order to control the molecular weight and itsdistribution, an olefin can be used as a chain transfer agent. Examplesof the olefin include α-olefins such as ethylene, propylene, 1-butene,1-pentene, 1-hexene, 1-octene, or fluorine-containing olefins thereof,silicon-containing olefins such as vinyltrimethylsilane,allyltrimethylsilane, allyltriethylsilane, allyltriisopropylsilane, orfluorine- and silicon-containing olefins thereof, and examples of thediene include non-conjugated dienes such as 1,4-pentadiene,1,5-hexadiene, 1,6-heptadiene, or fluorine-containing non-conjugateddienes. Further, these olefins, fluorine-containing olefins, dienes, orfluorine-containing dienes may be each used individually or incombination of two or more kinds thereof.

The amount of the olefin, fluorine-containing olefin, diene, orfluorine-containing diene to be used is such that the amount of theolefin or diene is in the range from usually 0.001 to 1,000 moles, andpreferably 0.01 to 100 moles, with respect to one mole of thefluorine-containing cyclic olefin monomer. Further, the amount of theolefin or diene is in the range from usually 0.1 to 1,000 moles, andpreferably 1 to 500 moles, with respect to one mole of the transitionmetal alkylidene catalyst.

Furthermore, the ring-opening metathesis polymerization of thefluorine-containing cyclic olefin monomer can be performed in a solventor without a solvent, but examples of the particularly used solventinclude ethers such as tetrahydrofuran, diethyl ether, dibutyl ether,dimethoxyethane, dioxane, esters such as ethyl acetate, propyl acetate,butyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene orethyl benzene, and the like, aliphatic hydrocarbons such as pentane,hexane, heptane, aliphatic cyclic hydrocarbons such as cyclopentane,cyclohexane, methylcyclohexane, dimethylcyclohexane, decalin,halogenated hydrocarbons such as methylene dichloride, dichloroethane,dichloroethylene, tetrachloroethane, chlorobenzene, trichlorobenzene,fluorine-containing aromatic hydrocarbons such as fluorobenzene,difluorobenzene, hexafluorobenzene, trifluoromethylbenzene, meta-xylenehexafluoride, fluorine-containing aliphatic hydrocarbons such asperfluorohexane, fluorine-containing aliphatic cyclic hydrocarbons suchas perfluorocyclodecalin, and fluorine-containing ethers such asperfluoro-2-butyl tetrahydrofuran. These may be used in combination oftwo or more kinds thereof.

Although varying depending on the reactivity of the monomer and thesolubility in solvent used for the polymerization, the ring-openingmetathesis polymerization of the fluorine-containing cyclic olefinmonomer can be carried out under the condition where the concentrationof the fluorine-containing cyclic olefin monomer relative to the monomersolution is usually in the range from 5 to 100% by mass, and preferablyin the range from 10 to 60% by mass, the reaction temperature is usuallyin the range from −30 to 150° C., and preferably in the range from 30 to100° C., and the reaction time is usually in the range from 10 minutesto 120 hours, and preferably in the range from 30 minutes to 48 hours.Further, the reaction can be stopped with an inactivating agentincluding aldehydes such as butyl aldehyde, ketones such as acetone andthe like, alcohols such as methanol and the like, or water, therebyobtaining a solution of the polymer.

The fluorine-containing cyclic olefin polymer or the fluorine-containingcyclic olefin copolymer of the present invention can be obtained bysubjecting the fluorine-containing cyclic olefin monomer to ring-openingmetathesis polymerization, and then subjecting the olefin portion in themain chain of the resulting polymer to a hydrogenation reaction.Further, the hydrogenation catalyst may be either a homogeneous metalcomplex catalyst or a heterogeneous metal-supported catalyst, which doesnot cause a hydrogenation reaction of the solvent used and is capable ofsubjecting the olefin portion in the main chain of the resulting polymerto hydrogenation reaction. Examples of the homogeneous metal complexcatalyst include chlorotris(triphenylphosphine)rhodium,dichlorotris(triphenylphosphine)osmium,dichlorohydridobis(triphenylphosphine)iridium,dichlorotris(triphenylphosphine)ruthenium,dichlorotetrakis(triphenylphosphine)ruthenium,chlorohydridocarbonyltris(triphenylphosphine)ruthenium,dichlorotris(trimethylphosphine)ruthenium, and the like, and examples ofthe heterogeneous metal-supported catalyst include activatedcarbon-supported palladium, alumina-supported palladium, activatedcarbon-supported rhodium, alumina-supported rhodium, and the like. Thesehydrogenation catalysts may be used individually or in combination oftwo or more kinds thereof.

When the olefin portion in the main chain is subjected to ahydrogenation treatment, in the case of using a known heterogeneous orhomogeneous hydrogenation catalyst, the amount of the hydrogenationcatalyst to be used is one such that the amount of the metal componentin the hydrogenation catalyst is usually from 5×10⁻⁴ parts by mass to100 parts by mass, and preferably from 1×10⁻² parts by mass to 30 partsby mass, with respect to 100 parts by mass of the polymer before thehydrogenation treatment.

The solvent used for hydrogenation is not particularly limited as longas it is one in which a fluorine-containing cyclic olefin polymer or afluorine-containing cyclic olefin copolymer is dissolved and the solventitself is not hydrogenated, and examples thereof include ethers such astetrahydrofuran, diethyl ether, dibutyl ether, dimethoxyethane, esterssuch as ethyl acetate, propyl acetate, butyl acetate, aromatichydrocarbons such as benzene, toluene, xylene, ethyl benzene, aliphatichydrocarbons such as pentane, hexane, heptane, aliphatic cyclichydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane,dimethylcyclohexane, decalin, halogenated hydrocarbons such as methylenedichloride, chloroform, dichloroethane, dichloroethylene,tetrachloroethane, chlorobenzene, trichlorobenzene, fluorine-containingaromatic hydrocarbons such as fluorobenzene, difluorobenzene,hexafluorobenzene, trifluoromethylbenzene, meta-xylene hexafluoride,fluorine-containing aliphatic hydrocarbons such as perfluorohexane,fluorine-containing aliphatic cyclic hydrocarbons such asperfluorocyclodecalin, and fluorine-containing ethers such asperfluoro-2-butyltetrahydrofuran and the like. These solvents may beused in combination of two or more kinds thereof.

The hydrogenation reaction of the olefin portion in the main chain iscarried out at a hydrogen pressure in the range from normal pressure to30 MPa, preferably from 0.5 to 20 MPa, and particularly preferably from2 to 15 MPa, the reaction temperature is a temperature in the range fromusually 0 to 300° C., preferably room temperature to 250° C., andparticularly preferably 50 to 200° C. The mode in which thehydrogenation reaction is carried out is not particularly limited, butexamples thereof include a method in which a catalyst is dispersed anddissolved in a solvent to carry out a hydrogenation reaction, a methodin which a catalyst is charged into a column or the like, and then apolymer solution is flowed as a mobile phase, and the like.

Furthermore, the hydrogenation treatment of the olefin portion in themain chain is not particularly limited, and thus it may be carried outby precipitating the polymerization solution of the fluorine-containingcyclic olefin polymer (A) before the hydrogenation treatment into a poorsolvent, isolating the polymer, and then dissolving the polymer in asolvent to carry out a hydrogenation treatment, or the hydrogenationtreatment may be carried out with a hydrogenation catalyst while notisolating the polymer from the polymerization solution.

Moreover, the hydrogenation rate of the olefin portion of thefluorine-containing cyclic olefin polymer (A) is 50% or more, preferablyfrom 70 to 100%, and more preferably from 90 to 100%. If thehydrogenation rate is less than 50%, the olefin portion may causedeterioration of heat resistance or weather resistance due to oxidationor deterioration by light absorption.

In the present invention, in the case where the polymer solution (resincomposition for transcription) is brought into contact with a mold, thefluorine-containing cyclic olefin polymer (A) may be dissolved in asolvent after recovered from the hydrogenated polymer solution, and thenbrought into contact with mold; while not recovering thefluorine-containing cyclic olefin polymer (A), the hydrogenated polymersolution may be brought into contact with a mold; or two or more kindsof solvents are mixed with the hydrogenated polymer solution and broughtinto contact with a mold. A method for recovering thefluorine-containing cyclic olefin polymer (A) from the hydrogenatedpolymer solution is not particularly limited, but examples thereofinclude a method in which a reaction solution is discharged into a poorsolvent under stirring, a method in which a polymer is precipitated by aprocess such as a steam-stripping process for blowing steam into areaction solution, and recovered by a process of filtration,centrifugation, decantation or the like, or a method in which a solventis evaporated off from a reaction solution by heating or the like, andthe like. Further, within a range not impairing the purpose of thepresent invention, known various additives such as an ultravioletabsorber, an antioxidant, a flame retardant, an antistatic agent can beblended with the recovered polymer.

<Photocurable Compound (B)>

In the present invention, the composition of the fluorine-containingcyclic olefin polymer (A) and the photocurable compound (B) is one suchthat the mass ratio (A)/(B) is in the range from usually 99.9/0.1 to80/20, preferably 99.9/0.1 to 90/10, and more preferably 99.9/0.1 to95/5. If the percentage by mass of the photocurable compound (B) is morethan 20%, the light transmittance in the visible light region may beless than BO % in some cases.

Examples of the photocurable compound (B) include a compound having areactive double bond group, a cationically ring-opening polymerizablecompound, and the like. These compounds may have one or plural reactivegroups in one molecule, but the compounds having two or more reactivegroups in one molecule are preferably used. The compounds havingdifferent numbers of the reactive groups may be mixed at any ratio andthen used, or a compound having a reactive double bond group and acationically ring-opening polymerizable compound may be mixed at anyratio and then used. By this these, the coatability when coating thefluorine-containing cyclic olefin polymer composition on a patternsurface of the mold and curability during curing with light irradiationare optimized, and as a result, a three-dimensional network structurecan be formed with high efficiency inside and over the surface of theimprint product, and thus, a nanoimprint film having a fine patternformed over its surface, having a high surface hardness, can be formed.

Among the photocurable compounds (B), examples of the compound having areactive double bond group include olefins such as fluorodienes(CF₂═CFOCF₂CF₂CF═CF₂, CF₂═CFOCF₂CF(CF₃) CF═CF₂, CF₂═CFCF₂C(OH)(CF₃)CH₂CH═CH₂, CF₂═CFCF₂C(OH)(CF₃) CH═CH₂,CF₂═CFCF₂C(CF₃)(OCH₂OCH₃)CH₂CH═CH₂, CF₂═CFCH₂C(C(CF₃)₂OH)(CF₃)CH₂CH═CH₂,and the like);

cyclic olefins such as norbornene, norbornadiene;

alkyl vinyl ethers such as cyclohexylmethyl vinyl ether, isobutyl vinylether, cyclohexyl vinyl ether, ethyl vinyl ether;

vinyl esters such as vinyl acetate; and

(meth)acrylic acids and derivatives thereof, or fluorine-containingacrylates thereof, such as (meth)acrylic acid, phenoxyethyl acrylate,benzyl acrylate, stearyl acrylate, lauryl acrylate, 2-ethyl hexylacrylate, allyl acrylate, 1,3-butanediol diacrylate, 1,4-butanedioldiacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate,pentaerythritol triacrylate, dipentaerythritol hexaacrylate, ethoxyethylacrylate, methoxyethyl acrylate, glycidyl acrylate,tetrahydrofurfurylacrylate, diethylene glycol diacrylate, neopentylglycol diacrylate, polyoxyethylene glycol diacrylate, tripropyleneglycol diacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,4-hydroxybutyl vinyl ether, N,N-diethylaminoethyl acrylate,N,N-dimethylaminoethyl acrylate, N-vinyl pyrrolidone, dimethylaminoethylmethacrylate, and the like.

More preferable examples thereof include trifunctional or higheracrylates represented by the general formulae (5), (6), (7), and (8).These may be used individually or in combination of two or more kindsthereof. By using a (meth)acrylate monomer having a trifunctional orhigher reactive double bond group, it is possible to form athree-dimensional network structure with high efficiency after curingwith light irradiation.

In the formula (5), R¹² represents tolylene, diphenylmethane,hexamethylene, norbornane dimethylene, dicyclohexylenemethane,trimethylcyclohexylene, cyclohexane dimethylene,N,N′,N″-tris(hexamethylene)-isocyanurate, N,N′-dihexamethyleneurea,N,N,N′-tris(hexamethylene)-urea, N,N,N′,N′-tetrakis(hexamethylene)-urea,or xylene. R⁹, R¹⁰, and R¹¹ independently represent H or CH₃. W¹ and W²represent H, CH₃, OH, or V¹. X¹ represents an integer of 2 to 4. Y¹represents an integer of 0 to 2 and Y² represents an integer of 0 to 5.

In the formula (6), R¹⁶ represents tolylene, diphenyl methane,hexamethylene, norbornanedimethylene, dicyclohexylenemethane,trimethylcyclohexylene, cyclohexane dimethylene, N,N′,N″-tris(hexamethylene)-isocyanurate, N,N′-dihexamethyleneurea,N,N,N′-tris(hexamethylene)-urea, N,N,N′,N′-tetrakis(hexamethylene)-urea,or xylene. R¹³, R¹⁴, and R¹⁵ independently represent H or CH₃. W³ and W⁴represent H, CH₃, OH, or V². X² represents an integer of 2 to 4. Y³represents an integer of 0 to 2, and Y⁴ represents an integer of 0 to 5.

In the formula (7), W⁵ represents H, CH₃, OH, or V³. R¹⁷, R¹⁸, and R¹⁹independently represent H or CH₃, and Y⁵ represents an integer of 0 to20.

In the formula (8), W⁶ and W⁷ represent H, CH₃, OH, or V⁴. R²⁰, R²¹, andR²² represent H or CH₃, and Y⁶ represents an integer of 0 to 3.

Furthermore, among the photocurable compounds (B), examples of thecationically ring-opening polymerizable compound include epoxy compoundssuch as cyclohexene epoxide, dicyclopentadiene oxide, limonene dioxide,4-vinylcyclohexene dioxide,3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate,di(3,4-epoxycyclohexyl)adipate, (3,4-epoxycyclohexyl)methyl alcohol,(3,4-epoxy-6-methylcyclohexyl)methyl-3,4-epoxy-6-methylcyclohexanecarboxylate,ethylene 1,2-di(3,4-epoxycyclohexanecarboxylic acid) ester,(3,4-epoxycyclohexyl)ethyltrimethoxysilane, phenyl glycidyl ether,dicyclohexyl-3,3′-diepoxide, a bisphenol A type epoxy resin, ahalogenated bisphenol A type epoxy resin, a bisphenol F type epoxyresin, an o-, m-, or p-cresol novolak type epoxy resin, a phenol novolaktype epoxy resin, a polyglycidyl ether of a polyhydric alcohol, analicyclic epoxy resin such as3,4-epoxycyclohexenylmethyl-3′,4′-epoxycyclohexenecarboxylate, glycidylether of hydrogenation bisphenol A, and the like. Further examplesthereof include oxetane compounds such as3-methyl-3-(butoxymethyl)oxetane, 3-methyl-3-(pentyloxymethyl)oxetane,3-methyl-3-(hexyloxymethyl)oxetane,3-methyl-3-(2-ethylhexyloxymethyl)oxetane,3-methyl-3-(octyloxymethyl)oxetane,3-methyl-3-(decanoloxymethyl)oxetane,3-methyl-3-(dodecanoloxymethyl)oxetane,3-methyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(butoxymethyl)oxetane,3-ethyl-3-(pentyloxymethyl)oxetane, 3-ethyl-3-(hexyloxymethyl)oxetane,3-ethyl-3-(2-ethylhexyloxymethyl)oxetane,3-ethyl-3-(octyloxymethyl)oxetane, 3-ethyl-3-(decanoloxymethyl)oxetane,3-ethyl-3-(dodecanoloxymethyl)oxetane, 3-(cyclohexyloxymethyl)oxetane,3-methyl-3-(cyclohexyloxymethyl)oxetane,3-ethyl-3-(cyclohexyloxymethyl)oxetane,3-ethyl-3-(phenoxymethyl)oxetane, 3,3-dimethyloxetane,3-hydroxymethyloxetane, 3-methyl-3-hydroxymethyloxetane,3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane,3-n-propyl-3-hydroxymethyloxetane, 3-isopropyl-3-hydroxymethyloxetane,3-n-butyl-3-hydroxymethyloxetane, 3-isobutyl-3-hydroxymethyloxetane,3-sec-butyl-3-hydroxymethyloxetane, 3-tert-butyl-3-hydroxymethyloxetane,3-ethyl-3-(2-ethyl hexyl) oxetane, and the like, and for the compoundshaving two or more oxetanyl groups, bis(3-ethyl-3-oxetanylmethyl)ether,1,2-bis[(3-ethyl-3-oxetanylmethoxy)]ethane,1,3-bis[(3-ethyl-3-oxetanylmethoxy)]propane,1,3-bis[(3-ethyl-3-oxetanylmethoxy)]-2,2-dimethyl-propane,1,4-bis(3-ethyl-3-oxetanylmethoxy)butane,1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane,1,4-bis[(3-methyl-3-oxetanyl)methoxy]benzene,1,3-bis[(3-methyl-3-oxetanyl)methoxy]benzene,1,4-bis{[(3-methyl-3-oxetanyl)methoxy]methyl}benzene,1,4-bis{[(3-methyl-3-oxetanyl)methoxy]methyl}cyclohexane,4,4′-bis{[(3-methyl-3-oxetanyl)methoxy]methyl}biphenyl,4,4′-bis{[(3-methyl-3-oxetanyl)methoxy]methyl}bicyclohexane,2,3-bis[(3-methyl-3-oxetanyl)methoxy]bicyclo[2.2.1]heptane,2,5-bis[(3-methyl-3-oxetanyl)methoxy]bicyclo[2.2.1]heptane,2,6-bis[(3-methyl-3-oxetanyl)methoxy]bicyclo[2.2.1]heptane,1,4-bis[(3-ethyl-3-oxetanyl)methoxy]benzene,1,3-bis[(3-ethyl-3-oxetanyl)methoxy]benzene,1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene,1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}cyclohexane,4,4′-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}biphenyl,4,4′-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}bicyclohexane,2,3-bis[(3-ethyl-3-oxetanyl)methoxy]bicyclo[2.2.1]heptane,2,5-bis[(3-ethyl-3-oxetanyl)methoxy]bicyclo[2.2.1]heptane,2,6-bis[(3-ethyl-3-oxetanyl)methoxy]bicyclo[2.2.1]heptane, and the like.Further, these may be used individually or in combination of two or morekinds thereof.

Examples of the cationically ring-opening polymerizable compound includea trifunctional or higher epoxy compound represented by the generalformula (9). These may be used individually or in combination of two ormore kinds thereof. By using an epoxy monomer having a trifunctional orhigher epoxy group, it is possible to form a three-dimensional networkstructure with high efficiency after curing with light irradiation.

In the formula (9), W⁸ represents H, alkyl having 1 to 3 carbon atoms,OH, or V⁵, and Y⁷ represents an integer of 1 to 20.

Furthermore, examples of the photoradical initiator generating radicalsby light irradiation in the photocurable compound (B) includeacetophenones such as acetophenone, p-tert-butyltrichloroacetophenone,chloroacetophenone, 2,2-diethoxyacetophenone, hydroxyacetophenone,2,2-dimethoxy-2′-phenylacetophenone, 2-aminoacetophenone,dialkylaminoacetophenone; benzoins such as benzoin, benzoin methylether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutylether, 1-hydroxycyclohexylphenyl ketone,2-hydroxy-2-methyl-1-phenyl-2-methylpropan-1-one,1-(4-isopropylphenyl)-2-hydroxy-2-methyl propan-1-one; benzophenonessuch as benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate,methyl-o-benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone,hydroxypropylbenzophenone, acrylbenzophenone,4,4′-bis(dimethylamino)benzophenone; thioxanthones such as thioxanthone,2-chlorothioxanthone, 2-methylthioxanthone, diethylthioxanthone,dimethylthioxanthone; and fluorinated peroxides such asperfluoro(tert-butyl peroxide), perfluorobenzoyl peroxide; α-acyl oximeester, benzyl-(o-ethoxycarbonyl)-α-monooxime, acylphosphine oxide,glyoxyester, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone,tetramethylthiuram sulfide, azobisisobutyronitrile, benzoyl peroxide,dialkyl peroxide, tert-butylperoxy pivalate, and the like.

Specific examples of the more preferably used photoradical initiatorinclude Irgacure 651 (manufactured by Ciba Specialty ChemicalsCorporation), Irgacure 184 (manufactured by Ciba Specialty ChemicalsCorporation), Darocur 1173 (manufactured by Ciba Specialty ChemicalsCorporation), benzophenone, 4-phenylbenzophenone, Irgacure 500(manufactured by Ciba Specialty Chemicals Corporation), Irgacure 2959(manufactured by Ciba Specialty Chemicals Corporation) Irgacure 127(manufactured by Ciba Specialty Chemicals Corporation), Irgacure 907(manufactured by Ciba Specialty Chemicals Corporation), Irgacure 369(manufactured by Ciba Specialty Chemicals Corporation), Irgacure 1300(manufactured by Ciba Specialty Chemicals Corporation), Irgacure 819(manufactured by Ciba Specialty Chemicals Corporation), Irgacure 1800(manufactured by Ciba Specialty Chemicals Corporation), Darocur TPO(manufactured by Ciba Specialty Chemicals Corporation), Darocur 4265(manufactured by Ciba Specialty Chemicals Corporation), Irgacure OXE01(manufactured by Ciba Specialty Chemicals Corporation), Irgacure OXE02(manufactured by Ciba Specialty Chemicals Corporation), Esacure-KT55(manufactured by Lamberti S. P. A.), Esacure-KIP150 (manufactured byLamberti S. P. A.), Esacure-KIP100F (manufactured by Lamberti S. P. A.),Esacure-KT37 (manufactured by Lamberti S. P. A.) Esacure-KTO46(manufactured by Lamberti S. P. A.), Esacure-1001 M (manufactured byLamberti S. P. A.), Esacure-KIP/EM (manufactured by Lamberti S. P. A.),Esacure-DP250 (manufactured by Lamberti S. P. A.), Esacure-KB1(manufactured by Lamberti S. P. A.), and 2,4-diethylthioxanthone. Amongthese, examples of the even more preferably used photoradicalpolymerization initiator include Irgacure 184 (manufactured by CibaSpecialty Chemicals Corporation), Darocur 1173 (manufactured by CibaSpecialty Chemicals Corporation), Irgacure 500 (manufactured by CibaSpecialty Chemicals Corporation), Irgacure 819 (manufactured by CibaSpecialty Chemicals Corporation), Darocur TPO (manufactured by CibaSpecialty Chemicals Corporation), Esacure-KIP100F (manufactured byLamberti S. P. A.), Esacure-KT37 (manufactured by Lamberti S. P. A.),and Esacure-KTO46 (manufactured by Lamberti S. P. A.). Further, thesephotoradical initiators may be used individually or in combination oftwo or more kinds thereof.

<Photocuring Initiator (C)>

Examples of the photocuring initiator (photopolymerization initiator)(C) include a photoradical initiator that generates radicals by lightirradiation, a photocationic initiator that generates cations by lightirradiation, and the like. The amount of the photocuring intiator (C) tobe used is usually preferably 0.05 parts by mass or more, and morepreferably from 0.1 to 10 parts by mass, with respect to 100 parts bymass of the photocurable compound (B).

Among the photocuring initiators (C), the photocationic initiator thatgenerates cations by light irradiation is not particularly limited aslong as it is a compound that initiates the cation polymerization of theabove-described ring-opening polymerizable compounds that arecationically polymerizable with light irradiation, but, for example, acompound that discharges Lewis acids by performing a photoreaction, aswith an onium salt with an anion that pairs with an onium cation ispreferable.

Specific examples of the onium cation include diphenyliodonium,4-methoxydiphenyliodonium, bis(4-methylphenyl)iodonium,bis(4-tert-butylphenyl)iodonium, bis(dodecylphenyl)iodonium,triphenylsulfonium, diphenyl-4-thiophenoxyphenylsulfonium,bis[4-(diphenylsulfonio)-phenyl]sulfide,bis[4-(di(4-(2-hydroxyethyl)phenyl)sulfonio)-phenyl]sulfide,η5-2,4-(cyclopentadienyl)[1,2,3,4,5,6-η-(methylethyl)benzene]-iron (1+),and the like, and further include, in addition to the onium cations,perchlorate ions, trifluoromethane sulfonate ions, toluene sulfonateions, trinitrotoluene sulfonate ions, and the like. Further, thesephotocationic initiators may be used individually or in combination oftwo or more kinds thereof.

On the other hand, specific examples of the anion includetetrafluoroborate, hexafluorophosphate, hexafluoroantimonate,hexafluoroarsenate, hexachloroantimonate, tetra(fluorophenyl)borate,tetra(difluorophenyl)borate, tetra(trifluorophenyl)borate,tetra(tetrafluorophenyl)borate, tetra(pentafluorophenyl)borate,tetra(perfluorophenyl)borate, tetra(trifluoromethylphenyl)borate,tetra(di(trifluoromethyl)phenyl)borate, and the like. Further, thesephotocationic initiators may be used individually or in combination oftwo or more kinds thereof.

Specific examples of the more preferably used photocationic initiatorinclude Irgacure 250 (manufactured by Ciba Specialty ChemicalsCorporation), Irgacure 784 (manufactured by Ciba Specialty ChemicalsCorporation), Esacure-1064 (manufactured by Lamberti S. P. A.), CYRAUREUVI6990 (manufactured by Union Carbide Corporation), ADEKA OPTOMERSP-172 (manufactured by Adeka Corporation), ADEKA OPTOMER SP-170(manufactured by Adeka Corporation), ADEKA OPTOMER SP-152 (manufacturedby Adeka Corporation), and ADEKA OPTOMER SP-150 (manufactured by AdekaCorporation). Further, these photocationic initiators may be usedindividually or in combination of two or more kinds thereof.

The photocurable compound (B) and the photocuring initiator (C) can beused in the form of a photocurable composition containing them. Thephotocurable composition can be obtained by dissolving the photocuringinitiator (C) in the photocurable compound (B) itself or by dissolvingboth the photocurable compound (B) and the photocuring initiator (C) inan organic solvent. In addition, if necessary, other known components,for example, modifiers such as an anti-aging agent, a leveling agent, awettability improver, a surfactant, a plasticizer, stabilizers such asan ultraviolet absorber, a preservative, an antimicrobial agent, aphotosensitizing agent, a silane coupling agent, and the like may beused as a third component.

The organic solvent used for the preparation of a photocurablecomposition is not particularly limited, but examples thereof includefluorine-containing aromatic hydrocarbons such as meta-xylenehexafluoride, benzotrifluoride, fluorobenzene, difluorobenzene,hexafluorobenzene, trifluoromethyl benzene, bis(trifluoromethyl)benzene,meta-xylene hexafluoride, fluorine-containing aliphatic hydrocarbonssuch as perfluorohexane, perfluorooctane, fluorine-containing aliphaticcyclic hydrocarbons such as perfluorocyclodecalin, fluorine-containingethers such as perfluoro-2-butyl tetrahydrofuran, halogenatedhydrocarbons such as chloroform, chlorobenzene, trichlorobenzene, etherssuch as tetrahydrofuran, dibutyl ether, 1,2-dimethoxyethane, dioxane,propylene glycol mono methyl ether, dipropylene glycol monomethyl ether,propylene glycol monomethyl ether acetate, esters such as ethyl acetate,propyl acetate, butyl acetate, ketones such as methylethyl ketone,methylisobutyl ketone, cyclohexanone, and alcohols such as methanol,ethanol, isopropyl alcohol, 2-methoxyethanol, 3-methoxypropanol, and thelike. The organic solvent can be selected from these allowing for adissolving property and a film-forming property, and may be the same asor different from the organic solvent in which the fluorine-containingcyclic olefin polymer (A) is dissolved. Particularly, from the viewpointof a film-forming property, a solvent having a boiling point of 70° C.or higher at atmospheric pressure is preferred. If the boiling point ofthe solvent is low, for example, the evaporation speed is high and thesolvent starts to dry partially during coating, which causesdeterioration of film thickness precision or generation of fish eyes onthe film surface.

The fluorine-containing cyclic olefin polymer composition in the presentinvention can make to form a hydrogen bond between the molecules or inthe molecule due to using a specific fluorine-containing cyclic olefinpolymer having a hydrocarbon structure in the main chain and afluorine-containing aliphatic ring structure in the side chain. Further,it can form a three-dimensional network structure inside and over thesurface of the imprint product after curing with light irradiation sincea photocurable compound and a photocuring initiator are used. By theseaction, the change in the elastic modulus and the shrinkage rate of theresin can be optimized when heating, cooling, and curing in theprocesses for producing a nanoimprint product, and also, the hardnesscan be further improved. Accordingly, by the fluorine-containing cyclicolefin polymer of the present invention, an imprint product having afine pattern over its surface can be formed, in which a fine pattern ofthe mold surface is transcribed with high dimensional precision andwhich has a high surface hardness, and further, an imprint producthaving a large area can be obtained by a simple process, in which theimprint product has an excellent releasability.

Moreover, in the case where an imprint product having athree-dimensional network structure inside or over its surface isimplemented in a device or the like, deformation and scratching of animprint pattern on the stress applied from the outside can be suppressedeffectively, and it is possible to impart an important function inpractical use.

[Method for Preparing Fluorine-Containing Cyclic Olefin PolymerComposition]

As for the method for preparing the fluorine-containing cyclic olefinpolymer composition in the present invention, the fluorine-containingcyclic olefin polymer composition can be obtained simply by preparingthe fluorine-containing cyclic olefin polymer (A) in a solution at anyconcentration in advance, and then adding a photocurable composition togive a mass ratio (A)/(B) of the fluorine-containing cyclic olefinpolymer (A) to the photocurable compound (B) in the range from usually99.9/0.1 to 5/95, preferably 99.9/0.1 to 10/90, more preferably 99.9/0.1to 80/20, and particularly preferably 99.9/0.1 to 50/50, and uniformlymixing them.

Furthermore, the photocurable composition can be prepared using thephotocurable compound (B) as a substitute for a solvent, while not usingthe organic solvent. In the case where the composition is prepared usingthe organic solvent, the concentration of the fluorine-containing cyclicolefin polymer (A) with respect to the solution is in the range fromusually 5 to 90% by mass, and preferably 10 to 60% by mass, and aconcentration that is efficiently and highly suitable for a polymerthickness optimal or coatability, or the like for the mold afterevaporation of the solvent.

The organic solvent used in the preparation of the fluorine-containingcyclic olefin polymer composition is not particularly limited, and thusthe same as the organic solvent used in the preparation of thephotocurable monomer composition may be used. Particularly, from thepoint of view of a film-forming property, a solvent having a boilingpoint of 70° C. or higher at atmospheric pressure is preferable, and ifthe boiling point of the solvent is low, for example, the evaporationspeed is high and the solvent starts to dry partially during coating,which causes deterioration of film thickness precision or generation offish eyes on the film surface.

In addition, in a similar way to the above-described photocurablecomposition, if necessary, other known components, for example,modifiers such as an anti-aging agent, a leveling agent, a wettabilityimprover, a surfactant, a plasticizer, stabilizers such as anultraviolet absorber, a preservative, an antimicrobial agent, aphotosensitizing agent, and a silane coupling agent may be added as athird component.

[Method for Producing Imprint Product]

The shapes of the convex portion and the concave portion of the moldhaving a fine pattern over its surface, which is used in the method forproducing a imprint product of the present invention, is notparticularly limited, but examples thereof include a rectangular shape,a cylindrical shape, a prismatic shape, a triangular cone shape, apolyhedral shape, a hemispherical shape, and the like. Further, examplesof the cross-sectional shape of the convex portion and the concaveportion include a rectangular cross-sectional shape, a triangularcross-sectional shape, a semi-circular cross-sectional shape, and thelike. Specific examples of the fine pattern of the imprint product ofthe mold preferably include a pattern in which a shape satisfying theabove-described conditions has a concavity and convexity structure, andthe like. These patterns are not particularly limited, and thus, may bearranged in a row at regular intervals or in any combination ofnon-contiguous arrangement and non-uniformly spaced arrangement.

The width of the convex portion and/or concave portion of the finepattern is usually from 10 nm to 50 μm, and preferably from 20 nm to 1μm. Further, the depth of the concave portion is usually from 30 nm to50 μm, and preferably from 50 nm to 1 μm. Further, the ratio of thewidth of the convex portion to the depth of the concave portion, thatis, the aspect ratio, is usually from 0.1 to 500, and preferably from0.5 to 20.

Examples of the material for the mold base material used for theproducing of the nanoimprint product by using the fluorine-containingcyclic olefin polymer composition (solution) of the present inventioninclude metal materials such as nickel, iron, stainless steel,germanium, titanium, silicone, inorganic materials such as glass,quartz, alumina resin materials such as polyimide, polyamide, polyester,polycarbonate, polyphenylene ether, polyphenylene sulfide, polyacrylate,polymethacrylate, polyarylate, an epoxy resin, a silicone resin, andcarbon materials such as diamond, graphite, and the like.

Moreover, the method for bringing the fluorine-containing cyclic olefinpolymer composition (solution) of the present invention into contactwith the mold is not particularly limited, but it may be, for example,either a method in which a polymer solution is coated on the finepattern surface of a mold by a process of table coating, spin coating,dip coating, die coating, spray coating, bar coating, roll coating,curtain flow coating, or the like, or a method in which a polymersolution is coated on a base material including metal materials such asstainless steel, silicone, inorganic materials such as glass, quartz,and resin materials such as polyimide, polyamide, polyester,polycarbonate, polyphenylene ether, polyphenylene sulfide, polyacrylate,polymethacrylate, polyarylate, an epoxy resin, a silicone resin, by aprocess of table coating, spin coating, dip coating, die coating, spraycoating, bar coating, roll coating, curtain flow coating, or the like,on which the fine pattern surface of the mold is then covered, therebybringing them into contact with each other.

Specific examples of the method comprise:

(1) a method comprising a step of coating the fluorine-containing cyclicolefin polymer composition of the present invention over the surface ofa mold having a fine pattern over its surface, and a step of heating thecoated composition, followed by light irradiation, to cure thecomposition,

(2) a method comprising coating a fluorine-containing cyclic olefinpolymer composition over a support (base material) to form a coatingfilm, a step of pressing the upper surface of the coating film over themold surface having a fine pattern thereon, and a step of heating thecoating film pressed over the mold surface, followed by lightirradiation, to cure the coating film,

and the like. In addition, in the (2) method, it is also possible forthe solvent to be evaporated from the coating film, and then the coatingfilm be pressed onto the mold.

The film thickness on the mold after bringing the fluorine-containingcyclic olefin polymer composition into contact with the mold, followedby heating and curing with light irradiation is not particularlylimited, but it is preferably from 1 μm to 10 mm, more preferably from 5μm to 1 mm, and most preferably from 10 μm to 0.5 mm. Within theseranges, an independent imprint product can be obtained.

The heating of the film on the mold at that time can be carried out at atemperature in the range from usually 10 to 300° C., and preferably 50to 200° C. and a pressure in the range from 133 Pa to atmosphericpressure, for a heating time in the range from usually 10 minutes to 120hours, and preferably in the range from 30 minutes to 48 hours. Further,the heating temperature, pressure, and time may each vary stepwise bysetting each of them.

The light to be irradiated is not particularly limited as long as lightirradiation can give energy for causing a radical reaction or an ionreaction with a photocuring initiator. As this light source, a lightbeam having a wavelength of 400 nm or less, for example, a low-pressuremercury lamp, a medium-pressure mercury lamp, a high-pressure mercurylamp, an ultrahigh pressure mercury lamp, a chemical lamp, a black lightlamp, a microwave excitation mercury lamp, and a metal halide lamp,i-rays, G-rays, KrF excimer laser light, or ArF excimer laser light canbe used.

The irradiation intensity to the fluorine-containing cyclic olefinpolymer composition is controlled according to a product to be targeted,and thus, is not particularly limited. For example, the lightirradiation intensity of the light wavelength region effective foractivation of the photopolymerization initiator as described later(although varying depending on the photopolymerization initiator, butlight having a light irradiation intensity of 300 to 420 nm is usuallyused) is preferably 0.1 to 100 mW/cm². If the irradiation intensity forthe composition is less than 0.1 mW/cm², the reaction time is too long,whereas if it is more than 100 mW/cm², there is a concern that heatradiated from a lamp and heat generated during polymerization of thecomposition may reduce the cohesive force of the resulting curedproduct, cause yellowing, or cause deterioration of the support.

The light irradiation time is controlled according to a product to betargeted, and thus, is not particularly limited. However, an integratedlight quantity which is represented by a product of the lightirradiation intensity of alight wavelength region and alight irradiationtime can be usually set at 3 to 1000 mJ/cm², more preferably 5 to 500mJ/cm², and particularly preferably 10 to 300 mJ/cm². If the integratedlight quantity for the composition is less than 3 mJ/cm², generation ofactive species from the photopolymerization initiator is not sufficient,and there is a concern that the characteristics of the resulting curedproduct may be deteriorated, whereas if the integrated light quantityfor the composition is more than 1000 mJ/cm², improvement ofproductivity may be at disadvantage. In addition, it is sometimespreferable to use heating together with the process as above in order topromote the polymerization reaction. Further, the temperature in thecase of curing a curable resin by light irradiation is usuallypreferably from 0 to 150° C., and more preferably from 0 to 60° C.

In the present invention, an imprint product can be formed on a mold bybringing the fluorine-containing cyclic olefin polymer composition(solution) into contact with a mold having a fine pattern over itssurface, and evaporating volatile components such as a solvent byheating, followed by curing with light irradiation. The release of theimprint product from the mold is carried out at a temperature that ispreferably no higher than the glass transition temperature of thefluorine-containing cyclic olefin polymer (A), and more preferably, nohigher than (glass transition temperature −20° C.). By this, a patternshape formed on the imprint product with high precision can bemaintained and easily released. As for the releasing method, the imprintproduct can be released from the mold by peeling-off, or the mold andthe imprint product are brought into contact by a process of dipping,spraying, or the like, using a medium such as, for example, water andthen be released from each other using surface tension. In addition, aresin material or an inorganic material such as glass, may be attachedto the back side of the imprint product, and the substrate may bereleased as a support.

<Method for Producing Cured Body>

Moreover, a cured body can be obtained using an imprint product obtainedby using the fluorine-containing cyclic olefin polymer composition ofthe present invention as a replica mold.

Examples of the method for obtaining a cured body include a methodcomprising a step of bringing a surface having the fine pattern of theimprint product into contact with a photocurable monomer composition, astep of curing the photocurable monomer composition with lightirradiation to obtain a cured product, and a step of releasing the curedproduct from the imprint product.

The method for bringing the surface having the fine pattern of theimprint product into contact with the photocurable monomer compositionis not particularly limited, but it may be, for example, either a methodin which the photocurable monomer composition is coated on the finepattern surface of the imprint product by a process of table coating,spin coating, dip coating, die coating, spray coating, bar coating, rollcoating, curtain flow coating, or the like, or a method in which thephotocurable monomer composition is coated on a base material includingthe above-described metal materials, inorganic materials such as glass,quartz, and the like, resin materials, and the like, by a process oftable coating, spin coating, dip coating, die coating, spray coating,bar coating, roll coating, curtain flow coating, or the like, on whichthe fine pattern surface of the imprint product is then covered, therebybringing them into contact with each other.

The light to be irradiated to the photocurable monomer composition isnot particularly limited as long as light irradiation can give energyfor causing a radical reaction or an ion reaction with a photocuringinitiator in a similar way to the fluorine-containing cyclic olefinpolymer composition. As this light source, a light beam having awavelength of 400 nm or less, for example, a low-pressure mercury lamp,a medium-pressure mercury lamp, a high-pressure mercury lamp, anultrahigh pressure mercury lamp, a chemical lamp, a black light lamp, amicrowave excitation mercury lamp, and a metal halide lamp, i-rays,G-rays, KrF excimer laser light, or ArF excimer laser light can be used.

In a similar way to the fluorine-containing cyclic olefin polymercomposition, the irradiation intensity to the photocurable monomercomposition is controlled according to a product to be targeted, andthus, is not particularly limited. For example, the light irradiationintensity of the light wavelength region effective for activation of thephotopolymerization initiator as described later (although varyingdepending on the photopolymerization initiator, but light having a lightirradiation intensity of 300 to 420 nm is usually used) is preferablyfrom 0.1 to 100 mW/cm². If the irradiation intensity for the compositionis less than 0.1 mW/cm², the reaction time is too long, whereas if it ismore than 100 mW/cm², there is a concern that heat radiated from a lampand heat generated during polymerization of the composition may reducethe cohesive force of the resulting cured product, cause yellowing, orcause deterioration of the support.

In a similar way to the fluorine-containing cyclic olefin polymercomposition, the light irradiation time is controlled according to aproduct to be targeted, and thus, is not particularly limited. However,an integrated light quantity which is represented by a product of thelight irradiation intensity of a light wavelength region and a lightirradiation time can be usually set at 3 to 1000 mJ/cm², more preferably5 to 500 mJ/cm², and particularly preferably 10 to 300 mJ/cm². If theintegrated light quantity for the composition is less than 3 mJ/cm²,generation of active species from the photopolymerization initiator isnot sufficient, and there is a concern that the characteristics of theresulting cured product may be deteriorated, whereas if the integratedlight quantity for the composition is more than 1000 mJ/cm², improvementof productivity may be reduced. In addition, it is sometimes preferableto use heating together with the process as above in order to promotethe polymerization reaction. Further, the temperature in the case ofcuring a curable resin by light irradiation is usually preferably 0 to150° C., and more preferably 0 to 60° C.

The film thickness of the cured resin (cured product) obtained by lightirradiation is not particularly limited, but is preferably from 1 μm to10 mm, more preferably from 5 μm to 1 mm, and most preferably from 10 μmto 0.5 mm. Within these ranges, an independent cured product can beobtained.

Regarding releasing the cured product, the cured product may be releasedfrom the replica mold by peeling-off, or the imprint product of thereplica mold may be dissolved in the organic solvent, and then releasedtherefrom. In addition, a resin material an inorganic material, such asglass may be attached to the back side of the cured product or the backside of the imprint product of the replica mold, and the substrate maybe released as a support.

The release of the cured product by peeling-off is not particularlylimited, but the cured product and the imprint product can be broughtinto contact by a process of dipping, spraying, or the like, using amedium such as, for example, water, and then be released using surfacetension. Further, in the case of dissolving the imprint product in anorganic solvent and then separating, the organic solvent for theseparation is not particularly limited, but can be selected from, forexample, fluorine-containing aromatic hydrocarbons such as meta-xylenehexafluoride, benzotrifluoride, fluorobenzene, difluorobenzene,hexafluorobenzene, trifluoromethyl benzene, bis(trifluoromethyl)benzene,meta-xylene hexafluoride, fluorine-containing aliphatic hydrocarbonssuch as perfluorohexane, perfluorooctane, fluorine-containing aliphaticcyclic hydrocarbons such as perfluorocyclodecalin, fluorine-containingethers such as perfluoro-2-butyltetrahydrofuran, halogenatedhydrocarbons such as chloroform, chlorobenzene, trichlorobenzene, etherssuch as tetrahydrofuran, dibutyl ether, 1,2-dimethoxyethane, dioxane,esters such as ethyl acetate, propyl acetate, butyl acetate, and ketonessuch as methylisobutyl ketone, cyclohexanone, and the like, consideringthe solubility.

Examples of the photocurable monomer in the present invention includeresins including, for example, a compound having a reactive double bondgroup, a cationically ring-opening polymerizable compound, and the like,in a similar way to the photocurable compound component constituting thefluorine-containing cyclic olefin polymer composition. These compoundsmay have one or plural reactive groups in one molecule. In addition,examples of the photopolymerization initiator include a photoradicalinitiator that generates radicals by light irradiation, a photocationicinitiator that generates cations by light irradiation, and the like.

In the case of using a composition in which the photocurable compoundand the photocuring initiator are mixed, the amount of the photocuringinitiator to be used is preferably 0.05 parts by mass or more, and morepreferably 0.1 to 10 parts by mass, with respect to 100 parts by mass ofthe photocurable compound.

Specific examples of the compound having a reactive double bond groupinclude:

cyclic olefins such as norbornene, norbornadiene;

alkyl vinyl ethers such as cyclohexylmethyl vinyl ether, isobutyl vinylether, cyclohexyl vinyl ether, ethyl vinyl ether;

vinyl esters such as vinyl acetate;

(meth)acrylic acids and derivatives thereof, or fluorine-containingacrylates thereof, such as (meth)acrylic acid, phenoxyethyl acrylate,benzyl acrylate, stearyl acrylate, lauryl acrylate, 2-ethyl hexylacrylate, allyl acrylate, 1,3-butanediol diacrylate, 1,4-butanedioldiacrylate, 1,6-hexane diol diacrylate, trimethylolpropane triacrylate,pentaerythritol triacrylate, dipentaerythritol hexaacrylate, ethoxyethylacrylate, methoxyethyl acrylate, glycidyl acrylate, tetrahydrofurfurylacrylate, diethylene glycol diacrylate, neopontyl glycol diacrylate,polyoxyethylene glycol diacrylate, tripropylene glycol diacrylate,2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl vinylether, N,N-diethylaminoethyl acrylate, N,N-dimethylaminoethyl acrylate,N-vinyl pyrrolidone, dimethylaminoethyl methacrylate; and

fluorodienes (CF₂═CFOCF₂CF₂CF═CF₂, CF₂═CFOCF₂CF(CF₃)CF═CF_(2f)CF₂═CFCF₂C(OH)(CF₃)CH₂CH═CH₂, CF₂═CFCF₂C(OH)(CF₃)CH═CH₂,CF₂═CFCF₂C(CF₃)(OCH₂OCH₃) CH₂CH═CH₂, CF₂═CFCH₂C(C(CF₃)₂OH)(CF₃)CH₂CH═CH₂, and the like). These may be used individually or incombination of two or more kinds thereof.

Furthermore, specific examples of the cationically ring-openingpolymerizable compound include epoxy compounds such as cyclohexeneepoxide, dicyclopentadiene oxide, limonene dioxide, 4-vinylcyclohexenedioxide, 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate,di(3,4-epoxycyclohexyl)adipate, (3,4-epoxycyclohexyl)methyl alcohol,(3,4-epoxy-6-methylcyclohexyl)methyl-3,4-epoxy-6-methylcyclohexanecarboxylate, ethylene 1,2-di(3,4-epoxycyclohexanecarboxylic acid) ester,(3,4-epoxycyclohexyl)ethyltrimethoxysilane, phenyl glycidyl ether,dicyclohexyl-3,3′-diepoxide, a bisphenol A type epoxy resin, ahalogenated bisphenol A type epoxy resin, a bisphenol F type epoxyresin, an o-, m-, or p-cresol novolak type epoxy resin, a phenol novolaktype epoxy resin, a polyglycidyl ether of a polyhydric alcohol, analicyclic epoxy resin such as3,4-epoxycyclohexenylmethyl-3′,4′-epoxycyclohexene carboxylate, or epoxycompounds such as glycidyl ether of hydrogenation bisphenol A, and thelike;

oxetane compounds such as 3-methyl-3-(butoxymethyl)oxetane,3-methyl-3-(pentyloxymethyl)oxetane, 3-methyl-3-(hexyloxymethyl)oxetane,3-methyl-3-(2-ethylhexyloxymethyl)oxetane,3-methyl-3-(octyloxymethyl)oxetane,3-methyl-3-(decanoloxymethyl)oxetane,3-methyl-3-(dodecanoloxymethyl)oxetane,3-methyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(butoxymethyl)oxetane,3-ethyl-3-(pentyloxymethyl)oxetane, 3-ethyl-3-(hexyloxymethyl)oxetane,3-ethyl-3-(2-ethylhexyloxymethyl)oxetane,3-ethyl-3-(octyloxymethyl)oxetane, 3-ethyl-3-(decanoloxymethyl)oxetane,3-ethyl-3-(dodecanoloxymethyl)oxetane, 3-(cyclohexyloxymethyl)oxetane,3-methyl-3-(cyclohexyloxymethyl)oxetane,3-ethyl-3-(cyclohexyloxymethyl)oxetane,3-ethyl-3-(phenoxymethyl)oxetane, 3,3-dimethyloxetane,3-hydroxymethyloxetane, 3-methyl-3-hydroxymethyloxetane,3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane,3-n-propyl-3-hydroxymethyloxetane, 3-isopropyl-3-hydroxymethyloxetane,3-n-butyl-3-hydroxymethyloxetane, 3-isobutyl-3-hydroxymethyloxetane,3-sec-butyl-3-hydroxymethyloxetane, 3-tert-butyl-3-hydroxymethyloxetane,3-ethyl-3-(2-ethyl hexyl)oxetane, and the like;

compounds having two or more oxetanyl groups, such as oxetane compoundsincluding bis(3-ethyl-3-oxetanylmethyl)ether,1,2-bis[(3-ethyl-3-oxetanylmethoxy)]ethane,1,3-bis[(3-ethyl-3-oxetanylmethoxy)]propane,1,3-bis[(3-ethyl-3-oxetanylmethoxy)]-2,2-dimethyl-propane,1,4-bis(3-ethyl-3-oxetanylmethoxy)butane,1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane,1,4-bis[(3-methyl-3-oxetanyl)methoxy]benzene,1,3-bis[(3-methyl-3-oxetanyl)methoxy]benzene,1,4-bis{[(3-methyl-3-oxetanyl)methoxy]methyl}benzene,1,4-bis{[(3-methyl-3-oxetanyl)methoxy]methyl}cyclohexane,4,4′-bis{[(3-methyl-3-oxetanyl)methoxy]methyl}biphenyl,4,4′-bis{[(3-methyl-3-oxetanyl)methoxy]methyl}bicyclohexane,2,3-bis[(3-methyl-3-oxetanyl)methoxy]bicyclo[2.2.1]heptane,2,5-bis[(3-methyl-3-oxetanyl)methoxy]bicyclo[2.2.1]heptane,2,6-bis[(3-methyl-3-oxetanyl)methoxy]bicyclo[2.2.1]heptane,1,4-bis[(3-ethyl-3-oxetanyl)methoxy]benzene,1,3-bis[(3-ethyl-3-oxetanyl)methoxy]benzene,1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene,1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}cyclohexane,4,4′-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}biphenyl,4,4′-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}bicyclohexane,2,3-bis[(3-ethyl-3-oxetanyl)methoxy]bicyclo[2.2.1]heptane,2,5-bis[(3-ethyl-3-oxetanyl)methoxy]bicyclo[2.2.1]heptane,2,6-bis[(3-ethyl-3-oxetanyl)methoxy]bicyclo[2.2.1]heptane. Further,these may be used individually or in combination of two or more kindsthereof.

Furthermore, examples of the photoradical initiator that generatesradicals by light irradiation include acetophenones such asacetophenone, p-tert-butyltrichloroacetophenone, chloroacetophenone,2,2-diethoxyacetophenone, hydroxyacetophenone,2,2-dimethoxy-2′-phenylacetophenone, 2-aminoacetophenone,dialkylaminoacetophenone;

benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether,benzoin isopropyl ether, benzoin isobutyl ether,1-hydroxycyclohexylphonyl ketone, 2-hydroxy-2-methyl-1-phenyl-2-methylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl propan-1-one;

benzophenones such as benzophenone, benzoyl benzoic acid, methyl benzoylbenzoate, methyl-o-benzoyl benzoate, 4-phenylbenzophenone,hydroxybenzophenone, hydroxypropylbenzophenone, acrylbenzophenone,4,4′-bis(dimethylamino)benzophenone;

thioxanthones such as thioxanthone, 2-chlorothioxanthone,2-methylthioxanthone, diethylthioxanthone, dimethylthioxanthone;

fluorine-based peroxides such as perfluoro(tert-butyl peroxide),perfluorobenzoyl peroxide;

α-acyloxime ester, benzyl-(o-ethoxycarbonyl)-α-monooxime, acylphosphineoxide, glyoxyester, 3-ketocoumarin, 2-ethylanthraquinone,camphorquinone, tetramethylthiuram sulfide, azobisisobutyronitrile,benzoyl peroxide, dialkyl peroxide, tert-butylperoxy pivalate, and thelike. Further, these photoradical initiators may be used individually orin combination of two or more kinds thereof.

The photocationic initiator that generates cations by light irradiationis not particularly limited as long as it is a compound that initiatesthe cation polymerization of the above-described ring-openingpolymerizable compounds that are cationically polymerizable with lightirradiation, but, for example, a compound that discharges Lewis acids byperforming a photoreaction, as with an onium salt with an anion thatpairs with an onium cation is preferable.

Specific examples of the onium cation include diphenyliodonium,4-methoxydiphenyliodonium, bis(4-methylphenyl)iodonium,bis(4-tert-butylphenyl)iodonium, bis(dodecylphenyl)iodonium,triphenylsulfonium, diphenyl-4-thiophenoxyphenylsulfonium,bis[4-(diphenylsulfonio)-phenyl]sulfide,bis[4-(di(4-(2-hydroxyethyl)phenyl)sulfonio)-phenyl]sulfide,η5-2,4-(cyclopentadienyl)[1,2,3,4,5,6-η-(methylethyl)benzene]-iron (1+),and the like and further include, in addition to the onium cations,perchlorate ions, trifluoromethane sulfonate ions, toluene sulfonateions, trinitrotoluene sulfonate ions, and the like.

On the other hand, specific examples of the anion includetetrafluoroborate, hexafluorophosphate, hexafluoroantimonate,hexafluoroarsenate, hexachloroantimonate, tetra(fluorophenyl)borate,tetra(difluorophenyl)borate, tetra(trifluorophenyl)borate,tetra(tetrafluorophenyl)borate, tetra(pentafluorophenyl)borate,tetra(perfluorophenyl)borate, tetra(trifluoromethylphenyl)borate,tetra(di(trifluoromethyl)phenyl)borate, and the like. Further, thesephotocationic initiators may be used individually or in combination oftwo or more kinds thereof.

Furthermore, in the present invention, in addition to the monomer havinga photocurable group and the photopolymerization initiator, other knowncomponents may be added, if necessary. Examples of such other componentsinclude modifiers such as an anti-aging agent, a leveling agent, awettability improver, a surfactant, a plasticizer, stabilizers such asan ultraviolet absorber, a preservative, an antimicrobial agent, aphotosensitizing agent, a silane coupling agent, a solvent.

In the present invention, it is also possible to use a thermosettingmonomer composition instead of the photocurable monomer composition. Inthe case of using the thermosetting monomer composition, it ispreferable to cure at a temperature that is no higher than the glasstransition temperature of the fluorine-containing cyclic olefin polymer(A), and if curing is performed at a temperature equal to or higher thanthe above temperature, the fine pattern may be deformed in some cases.

EXAMPLES

Hereinafter, the present invention will be described with reference tothe Examples, but is by no means limited thereto. Further, themeasurement method for analytical values of the prepared polymers, thenanoimprint molding method, and the observation method thereof inExamples will be described below.

[Weight Average Molecular Weight (Mw), Molecular Weight Distribution(Mw/Mn)]

By means of gel permeation chromatography (GPC) under the followingcondition, the weight average molecular weight (Mw) and the numberaverage molecular weight (Mn) of the polymer dissolved intetrahydrofuran (THF) or trifluoromethyltoluene (TFT) were measured withmolecular-weight calibration relative to polystyrene standards.

Detector: RI-2031 and 875-UV manufactured by JASCO Corp. or Model 270manufactured by Viscotec Corp., columns connected in series: ShodexK-806 M, 804, 803, 802. 5, column temperature: 40° C., flow rate: 1.0ml/minute, sample concentration: 3.0 to 9.0 mg/ml

[Hydrogenation Rate of Fluorine-Containing Cyclic Olefin Polymer (A)]

A powder of a ring-opening metathesis polymer which had been subjectedto a hydrogenation reaction was dissolved in deuterated chloroform, ordeuterated tetrahydrofuran, or a mixed solvent of hexafluorobenzene anddeuterated chloroform, and the hydrogenation rate was calculated fromthe integral value of the absorption spectrum derived from hydrogenbonded to the double bond carbons in the main chain at δ=4.5 to 7.0 ppm,using a 270 MHz-¹H-NMR spectrum.

[Compositional Ratio of Fluorine-Containing Cyclic Olefin Copolymer]

A powder of a ring-opening metathesis polymer which had been subjectedto a hydrogenation reaction was dissolved in deuterated tetrahydrofuran,or a mixed solvent of hexafluorobenzene and deuterated chloroform,followed by addition of orthodifluorobenzene thereto as a referencesubstance, and the composition ratio was calculated from the integralvalue of the signals derived from —CF at δ=−150 to −200 ppm, —CF₂ atδ=−100 to −150 ppm, and —CF₃ at δ=−60 to −100 ppm in the respective unitstructures of the general formula (1) and the general formula (2) withthe orthodifluorobenzene at δ=−139 ppm set as the reference signal,using a 373 MHz-¹⁹F-NMR spectrum.

[Fluorine Atom Content Rate]

The fluorine atom content rate was calculated by the following equation(1).Fluorine atom content rate (% by mass)=(Fn×19)×100/Fw  (1)

Herein, in equation (1), Fn represents Fn¹×(1−m)+Fn²×m, wherein mrepresents a molar proportion of the general formula (2), Fn¹ and Fn²represent the number of fluorine atoms in the structural unitrepresented by the general formula (1) and the general formula (2),respectively; Fw represents Fw¹×(1−m)+Fw²×m, wherein Fw¹ and Fw²represent the formula weight of the structural unit represented by thegeneral formula (1) and the general formula (2), respectively.

[Glass Transition Temperature]

A measurement sample was analyzed using DSC-50 manufactured by ShimadzuCorp., at 10° C./min as the heating rate of increase in temperatureunder a nitrogen atmosphere.

[Measurement of Dynamic Mechanical Analysis]

A measurement sample was analyzed using RSA-III manufactured by TAInstruments in a tensile mode and under a nitrogen atmosphere, under theconditions of a rate of temperature, increase of 3° C./min, an analysisfrequency of 1 Hz, and a measureable distance of a sample deformationbetween chucks in dynamic mechanical analyzer was set in the range of 0to 4.2 mm.

[Observation of SEM Pattern]

The observation of the line-and-space and the cross-section of a imprintfilm product to which a fine pattern had been transcribed, and themeasurement of film thickness were carried out by using a scanningelectron microscope JSM-6701F manufactured by JASCO Corp. (hereinafter,indicated as SEM). The width of the lines and spaces was obtained byselecting arbitrary the pattern of three points from a cross-sectionalphotograph of SEM, measuring the lines and spaces with the measurementposition set at one-half of the height, and calculating the averagevalue.

[Mold Used in Imprint]

A silicone mold manufactured by Kyodo International Inc. was used, andfor the mold dimensions, the width of a convex portion was denoted asL1, the equal distance between the convexes was denoted as L2, and theheight of the convex portion was denoted as L3, and portions including apattern having the dimensions of the mold A of L1=420 nm, L2=570 nm, andL3=1600 nm, respectively, and the dimensions of the mold B of L1-200 nm,L2-100 nm, and L3=160 nm, were used for evaluation of the transcriptionability.

[UV Curing]

For curing of the coating film, blue light at 320 to 390 nm (electrodeless discharge lamp⋅D bulb) was irradiated to cure, using the UVirradiator manufactured by Fusion UV Systems Japan K. K. as a lightsource.

[Measurement of Scratch Hardness of Film According to Pencil Method]

The scratch hardness under a load of 100 g was measured using a filmspin-coated on a glass substrate, in accordance with JIS K5600-5-4(pencil scratch test method).

[Measurement of Linear Expansion Coefficient of Film]

Using a TMASS120 manufactured by SII (Seiko Instrument Company), asample with dimensions of 4 mm (width)×10 mm (distance between thechucks) was cut from a film having a thickness of 9 to 10 μm peeled froma glass substrate on which the film had been coated, and by a tensilemode, the sample was heated from 20° C. to a temperature at which thesample was extended by 1 mm under a load of 1.0 g, at a temperatureincrease rate of 5 mm/min, and then measured. The linear expansioncoefficient was analyzed from the temperature in the range from asoftening point to a temperature at which the sample was extended by 1mm and the extension rate of the film.

[Measurement of UV Transmittance]

An independent film having a thickness of 7 to 9 μm, peeled from a glasssubstrate, on which the film had been coated, using a UV-3100Smanufactured by Shimadzu Corporation, and measured.

Example 1 Synthesis ofpoly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene)

To a solution of5,5,6-trifluoro-6-(trifluoromethyl)bicyclo[2.2.1]hept-2-ene (100 g) and1-hexene (268 mg) in tetrahydrofuran was added a solution ofMo(N-2,6-Pr^(i) ₂C₆H₃)(CHCMe₂Ph)(OCMe(CF₃)₂)₂ (70 mg) in tetrahydrofuransolution, followed by carrying out ring-opening metathesispolymerization at 70° C. The olefin portion of the polymer thus obtainedwas subjected to a hydrogenation reaction at 160° C. with palladiumalumina (5 g) to obtain a solution ofpoly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene) intetrahydrofuran.

The solution was added to methanol, and a white polymer was separated byfiltration and dried to obtain 99 g of a polymer. The hydrogenation ratewas 100%, the weight average molecular weight (Mw) was 127000, themolecular weight distribution (Mw/Mn) was 1.70, the glass transitiontemperature was 109° C., and the fluorine atom content rate was 52.3% bymass.

Subsequently, the obtained polymer powder after the hydrogenation washot-pressed to produce a hot-pressed sheet having a thickness of 0.37mm. As seen from the results of the measurement of the dynamicmechanical analysis by tensile mode, the storage modulus in the rangefrom 113° C. to 152° C. was from 5.81 to 0.57 MPa, the loss modulus inthe range from 117° C. to 152° C. was from 3.05 to 0.27 MPa, and thechange in the storage modulus and the change in the loss modulus withrespect to the temperature were −0.13 MPa/° C. and −0.08 MPa/° C.,respectively, in the flat variable region of the storage modulus or theloss modulus, at a temperature equal to or higher than the glasstransition temperature.

Example 2 Synthesis ofpoly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene)

In the same manner as in Example 1 except that the catalyst was changedto Mo(N-2,6-Pr^(i) ₂C₆H₃)(CHCMe₂Ph)(OBu^(t))₂ (50 mg),poly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentyleneethylene) wasobtained (98 g). The hydrogenation rate was 100%, the weight averagemolecular weight (Mw) was 83000, the molecular weight distribution(Mw/Mn) was 1.73, the glass transition temperature was 108° C., and thefluorine atom content rate was 52.3% by mass.

Subsequently, the obtained polymer powder after the hydrogenation washot-pressed to produce a hot-pressed sheet having a thickness of 0.37mm. As seen from the results of the measurement of the dynamicmechanical analysis by tensile mode, the storage modulus in the rangefrom 109° C. to 150° C. was from 4.98 to 0.58 MPa, the loss modulus inthe range from 113° C. to 150° C. was from 2.96 to 0.31 MPa, and thechange in the storage modulus and the change in the loss modulus withrespect to the temperature were −0.12 MPa/° C. and −0.07 MPa/° C.,respectively, in the flat variable region of the storage modulus or theloss modulus, at a temperature equal to or higher than the glasstransition temperature.

Example 3 Synthesis ofpoly(1,2-difluoro-1-trifluoromethyl-2-perfluoroethyl-3,5-cyclopentyleneethylene)

In the same manner as in Example 1 except that the monomer was changedto5,6-difluoro-5-trifluoromethyl-6-perfluoroethylbicyclo[2.2.1]hept-2-ene(50 g) and the catalyst was changed to Mo(N-2,6-Pr^(i)₂C₆H₃)(CHCMe₂Ph)(OBu^(t))₂ (17 mg),poly(1,2-difluoro-1-trifluoromethyl-2-perfluoroethyl-3,5-cyclopentyleneethylene)was obtained (49 g). The hydrogenation rate was 100%, the weight averagemolecular weight (Mw) was 95000, the molecular weight distribution(Mw/Mn) was 1.52, the glass transition temperature was 110° C., and thefluorine atom content rate was 59.7% by mass.

Subsequently, the obtained polymer powder after the hydrogenation washot-pressed to produce a hot-pressed sheet having a thickness of 0.37mm. As seen from the results of the measurement of the dynamicmechanical analysis by tensile mode, the storage modulus in the rangefrom 115° C. to 160° C. was from 5.01 to 0.55 MPa, the loss modulus inthe range from 119° C. to 160° C. was from 3.10 to 0.24 MPa, and thechange in the storage modulus and the change in the loss modulus withrespect to the temperature were −0.12 MPa/° C. and −0.07 MPa/° C.,respectively, in the flat variable region of the storage modulus or theloss modulus, at a temperature equal to or higher than the glasstransition temperature.

Example 4 Synthesis of5,5,6-trifluoro-6-(trifluoromethyl)bicyclo[2.2.1]hept-2-ene and8,8,9-trifluoro-9-(trifluoromethyl)-tetracyclo[4.4.0.1^(2,5).1^(7,10)]-3-dodecenecopolymer

To a solution of5,5,6-trifluoro-6-(trifluoromethyl)bicyclo[2.2.1]hept-2-ene (50 g) and8,8,9-trifluoro-9-(trifluoromethyl)-tetracyclo[4.4.0.1^(2,5).1^(7,10)]-3-dodecene(22 g) and 1-hexene (0.462 g) in tetrahydrofuran was added a solution ofMo(N-2,6-Pr^(i) ₂C₆H₃)(CHCMe₂Ph)(OBu^(t))₂ (33.9 mg) in tetrahydrofuran,followed by carrying out ring-opening metathesis polymerization at 70°C. The olefin portion of the polymer thus obtained was subjected to ahydrogenation reaction at 160° C. with palladium alumina (3.6 g) toobtain a solution of a5,5,6-trifluoro-6-(trifluoromethyl)bicyclo[2.2.1]hept-2-ene and8,8,9-trifluoro-9-(trifluoromethyl)-tetracyclo[4.4.0.1^(2,5).1^(7,10)]-3-dodecenecopolymer in tetrahydrofuran. The solution was added to methanol, andthe white polymer was separated by filtration and dried to obtain 71 gof the polymer. The hydrogenation rate was 100%, the weight averagemolecular weight (Mw) was 98000, the molecular weight distribution(Mw/Mn) was 2.51, the glass transition temperature was 129° C., thecompositional ratio [I]/[II] was 75/25, and the fluorine atom contentwas 49.2% by mass.

Subsequently, the obtained polymer powder after the hydrogenation washot-pressed to produce a hot-pressed sheet having a thickness of 0.37mm. As seen from the results of the measurement of the dynamicmechanical analysis by tensile mode, the storage modulus in the rangefrom 149° C. to 175° C. was from 4.78 to 0.39 MPa, the loss modulus inthe range from 154° C. to 175° C. was from 4.80 to 0.19 MPa, and thechange in the storage modulus and the change in the loss modulus withrespect to the temperature were −0.17 MPa/° C. and −0.22 MPa/° C.,respectively, in the flat variable region of the storage modulus or theloss modulus, at a temperature equal to or higher than the glasstransition temperature.

Example 5

Producing of Imprint Product

To 50 g of a solution in whichpoly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene) withMw=127000 synthesized in Example 1 was dissolved at a concentration of27% by mass in cyclohexanone was added 13.5 g of a solution including1.0% by mass of a UV-curable resin monomer represented by the generalformula (10) (U15-HA, manufactured by Shin-Nakamura Chemical Co., Ltd.)and 0.03% by mass of a photopolymerization initiator (Esacure-KTO46,manufactured by Lamberti Co.) in 2-methoxyethanol, and 20 mg of thesolution thus obtained was added dropwise onto the pattern of the moldA, and uniformly coated by spin coating.

Subsequently, it was dried at room temperature for 30 minutes undernitrogen gas flow, then dried at 180° C. for 30 minutes, and was cooledto room temperature. The curable resin was cured with UV irradiation ata light quantity of 500 mJ/cm², and then peeled from the mold to obtainan imprint product in the form of a film having a film thickness of 8μm, having a fine pattern transcribed thereon. The pattern was observedby means of SEM, and the results were as follows: L1=569 nm, L2=421 nm,and L3=1595 nm.

Furthermore, the pencil hardness of the film formed from the solutioncoated on the glass substrate was HB, the average transmittance at 345to 385 nm of the peeled film having a thickness of 9 μm was 92.9%, andthe linear expansion coefficient at a softening point in the range from107° C. to 124° C. of the film having a thickness of 9 μm was 0.52%/° C.

Example 6

To 50 g of a solution in which poly(l,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene) withMw=83000 synthesized in Example 2 was dissolved at a concentration of27% by mass in cyclohexanone was added 13.5 g of a solution including1.0% by mass of the UV-curable resin monomer and 0.03% by mass of thephotopolymerization initiator, each described in Example 5, in2-methoxyethanol, and 20 mg of the solution thus obtained was addeddropwise onto the pattern of the mold A, and uniformly coated by spincoating. Subsequently, it was dried at room temperature for 30 minutesunder nitrogen gas flow, then dried at 180° C. for 30 minutes, and wascooled to room temperature. The curable resin was cured with UVirradiation at a light quantity of 500 mJ/cm², and then peeled from themold to obtain an imprint product in the form of a film having a filmthickness of 7 μm and a fine pattern transcribed thereon. The patternwas observed by means of SEM, and the results were as follows: L1=571nm, L2=419 nm, and L3=1594 nm. Furthermore, the pencil hardness of thefilm formed from the solution coated on the glass substrate was HB, andthe average transmittance at 345 to 385 nm of the peeled film having athickness of 7 μm was 93.0%.

Example 7

In the same manner as in Example 5 except that the mold A was changed tothe mold B in Example 5, an imprint product in the form of a film wasproduced. The film thickness was 7 μm, and the results from SEMobservation of the pattern were as follows: L1=101 nm, L2=199 nm, andL3=161 nm.

Example 8

To 50 g of a solution in whichpoly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene) withMw=127000 synthesized in Example 1 was dissolved at a concentration of27% by mass in cyclohexanone was added 13.5 g of a solution including3.0% by mass of the UV-curable resin monomer and 0.09% by mass of thephotopolymerization initiator, each described in Example 5, in2-methoxyethanol, and 20 mg of the solution thus obtained was addeddropwise onto the pattern of the mold A, and uniformly coated by spincoating.

Subsequently, it was dried at room temperature for 30 minutes undernitrogen gas flow, then dried at 180° C. for 30 minutes, and was cooledto room temperature. The curable resin was cured with UV irradiation ata light quantity of 500 mJ/cm², and then peeled from the mold to obtainan imprint product in the form of a film having a film thickness of 9 μmand a fine pattern transcribed thereon. The pattern was observed bymeans of SEM, and the results were as follows: L1=571 nm, L2=419 nm, andL3=1594 nm. Furthermore, the pencil hardness of the film formed from thesolution coated on the glass substrate was F, the average transmittanceat 345 to 385 nm of the peeled film having a thickness of 10 μm was88.9%, and the linear expansion coefficient at a softening point in therange from 108° C. to 139° C. of the film having a thickness of 10 μmwas 0.31%/° C.

Example 9

By the same method as in Example 5 except that the UV-curable resinmonomer was changed to a monomer represented by the general formula (11)(PE-4A, manufactured by Kyoeisha Chemical Co., Ltd.), an imprint productin the form of a film having a film thickness of 8 μm and a fine patterntranscribed thereon was obtained. The pattern was observed by means ofSEM, and the results were as follows: L1=570 nm, L2=420 nm, and L3=1595nm. Furthermore, the pencil hardness of the film formed from thesolution coated on the glass substrate was HB, and the averagetransmittance at 345 to 385 nm of the peeled film having a thickness of8 μm was 94.2%.

Example 10

By the same method as in Example 5 except that the UV-curable resinmonomer was changed to a monomer represented by the general formula (12)(A-9530, manufactured by Shin-Nakamura Chemical Co., Ltd.), an imprintproduct in the form of a film having a film thickness of 9 μm and a finepattern transcribed thereon was obtained. The pattern was observed bymeans of SEM, and the results were as follows: L1=571 nm, L2=419 nm, andL3=1594 nm. Furthermore, the pencil hardness of the film formed from thesolution coated on the glass substrate was HB, and the averagetransmittance at 345 to 385 nm of the peeled film having a thickness of9 μm was 93.2%.

Example 11

By the same method as in Example 5 except that the UV-curable resinmonomer was changed to a UV-curable hard coating agent (FH-900,manufactured by DIC), an imprint product in the form of a film having afilm thickness of 8 μm and a fine pattern transcribed thereon wasobtained. The pattern was observed by means of SEM, and the results wereas follows: L1=570 nm, L2=420 nm, and L3=1595 nm. Furthermore, thepencil hardness of the film formed from the solution coated on the glasssubstrate was HB, and the average transmittance at 345 to 385 nm of thepeeled film having a thickness of 8 μm was 94.8%.

Example 12

To 50 g of a solution in whichpoly(1,2-difluoro-1-trifluoromethyl-2-perfluoroethyl-3,5-cyclopentyleneethylene) with Mw=95000 synthesized in Example 3 was dissolved at aconcentration of 20% by mass in cyclohexanone was added 13.5 g of asolution including 1.0% by mass of the UV-curable resin monomer and0.03% by mass of the photopolymerization initiator, each described inExample 5, in 2-methoxyethanol, and 20 mg of the solution thus obtainedwas added dropwise onto the pattern of the mold A, and uniformly coatedby spin coating.

Subsequently, it was dried at room temperature for 30 minutes undernitrogen gas flow, then dried at 180° C. for 30 minutes, and was cooledto room temperature. The curable resin was cured with UV irradiation ata light quantity of 500 mJ/cm², and then peeled from the mold to obtainan imprint product in the form of a film having a film thickness of 8 μmand a fine pattern transcribed thereon. The pattern was observed bymeans of SEM, and the results were as follows: L1-569 nm, L2=421 nm, andL3=1594 nm. Furthermore, the pencil hardness of the film formed from thesolution coated on the glass substrate was HB, and the averagetransmittance at 345 to 385 nm of the peeled film having a thickness of8 μm was 95.4%.

Example 13

To 50 g of a solution in which the 5,5,6-trifluoro-6-(trifluoromethyl)bicyclo[2.2.1]hept-2-ene and8,8,9-trifluoro-9-(trifluoromethyl)c-tetracyclo[4.4.0.1^(2,5).1^(7,10)]-3-dodecenecopolymer with Mw=98000 synthesized in Example 4 was dissolved at aconcentration of 27% by mass in cyclohexanone was added 13.5 g of asolution including 1.0% by mass of the UV-curable resin monomer and0.03% by mass of the photopolymerization initiator, each described inExample 5, in 2-methoxyethanol, and 20 mg of the solution thus obtainedwas added dropwise onto the pattern of the mold A, and uniformly coatedby spin coating.

Subsequently, it was dried at room temperature for 30 minutes undernitrogen gas flow, then dried at 180° C. for 30 minutes, and was cooledto room temperature. The curable resin was cured with UV irradiation ata light quantity of 500 mJ/cm², and then peeled from the mold to obtainan imprint product in the form of a film having a film thickness of 9 μmand a fine pattern transcribed thereon. The pattern was observed bymeans of SEM, and the results were as follows: L1=570 nm, L2=420 nm, andL3=1595 nm. Furthermore, the pencil hardness of the film formed from thesolution coated on the glass substrate was F, and the averagetransmittance at 345 to 385 nm of the peeled film having a thickness of9 μm was 92.1%.

Example 14

Production of Curable Acrylic Resin Imprint Product by Replica Mold

60 mg of a UV-curable acrylic resin (ARONIX, manufactured by ToagoseiCo., Ltd.) was uniformly coated on a quartz glass by bar coating.

Subsequently, the imprint product in the form of a film, obtained fromthe poly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene)composition produced in Example 5 as a replica mold was pressed andcovered so as to put its pattern surface onto the coated liquid film,and then irradiated with UV for 15 minutes from the back side of thereplica mold at room temperature (radiation quantity: 34 mJ/cm²). Byperforming the peeling from the mold after irradiation, an imprintproduct in the form of a film having a film thickness of 70 μm and afine pattern transcribed thereon, was obtained. The pattern was observedby means of SEM, and the results were as follows: L1=420 nm, L2=570 nm,and L3=1595 nm.

Example 15

Production of Curable Epoxy-Based Resin Imprint Product by Replica Mold

45 mg of a curable epoxy-based resin (a mixture of 40% by mass of4,4′-bis(7-oxabicyclo[4.1.0]heptan-3-yl), 50% by mass of3-ethyl-3-(phenoxymethyl)oxetane, and 10% by mass of1,4-bis[((3-ethyloxetan-3-yl)methoxy)methyl]benzene) with a sulfoniumsalt being used as an initiator was uniformly coated on a quartz glassby bar coating.

Subsequently, the imprint product in the form of a film, obtained fromthe poly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene)composition produced in Example 5 as a replica mold was pressed andcovered so as to put its pattern surface onto the coated liquid film,and then irradiated with UV for 15 minutes from the back side of thereplica mold at room temperature (radiation quantity: 34 mJ/cm²). Byperforming the peeling from the mold after irradiation, an imprintproduct in the form of a film having a film thickness of 60 μm and afine pattern transcribed thereon, was obtained. The pattern was observedby means of SEM, and the results were as follows: L1=421 nm, L2=569 nm,and L3=1596 nm.

Example 16

To 42 g of a solution in whichpoly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene) withMw=83000 synthesized in Example 2 was dissolved at a concentration of60% by mass in methylethyl ketone was added 8 g of a solution including0.8 g (1.6% by mass) of a UV-curable resin monomer represented by thegeneral formula (13) (DENACOL EX-411, manufactured by Nagase ChemtexCorporation), 7.0 g (14% by mass) of di[2-(3-oxetanyl)butyl]ether(manufactured by Toagosei Co., Ltd.), and 0.016 g (0.3% by mass) of aphotocation initiator (ADEKA OPTOMER SP-172, manufactured by AdekaCorporation) as a photopolymerization initiator in methylethyl ketone,and 20 mg of the coating liquid thus obtained was added dropwise ontothe pattern of the mold A, and uniformly coated by spin coating.

Subsequently, it was dried at 60° C. for 5 minutes and was cooled toroom temperature. The curable resin was cured with UV irradiation at alight quantity of 500 mJ/cm², and then peeled from the mold to obtain animprint product in the form of a film having a film thickness of 9 μmand a fine pattern transcribed thereon. The pattern was observed bymeans of SEM, and the results were as follows: L1=570 nm, L2=420 nm, andL3=1595 nm. Furthermore, the pencil hardness of the film having thesolution coated on the glass substrate was B, and the averagetransmittance at 345 to 385 nm of the peeled film having a thickness of8 μm was 94.2%.

Comparative Example 1

20 mg of a solution in whichpoly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene) withMw=127000 synthesized in Example 1 was dissolved at a concentration of20% by mass in cyclohexanone was added dropwise onto the pattern of themold A, and uniformly coated by spin coating.

Subsequently, it was dried at room temperature for 30 minutes undernitrogen gas flow, and then dried at 180° C. for 30 minutes. The moldwas cooled to room temperature under nitrogen, followed by performingthe peeling from the mold, to obtain an imprint product in the form of afilm having a film thickness of 8 μm and a fine pattern transcribedthereon. The pattern was observed by means of SEM, and the results wereas follows: L1=568 nm, L2=422 nm, and L3=1594 nm. Furthermore, thepencil hardness of the film having the solution coated on the glasssubstrate was 4B, the average transmittance at 345 to 385 nm of thepeeled film having a thickness of 10 μm was 95.1%, and the linearexpansion coefficient at a softening point in the range from 108° C. to118° C. of the film having a thickness of 9 μm was 0.93%/° C.

Comparative Example 2 Synthesis ofPoly(1-Trifluoromethyl-3,5-Cyclopentylene Ethylene) and Production ofImprint Product by Coating Method

In the same manner as in Example 1 except that the monomer was changedto 5-(trifluoromethyl) bicyclo[2.2.1]hept-2-ene (10 g),poly(1-trifluoromethyl-3,5-cyclopentylene ethylene) (9 g) was obtained.The hydrogenation rate was 100%, the weight average molecular weight(Mw) was 98000, the molecular weight distribution (Mw/Mn) was 1.17, theglass transition temperature was 47° C., and the fluorine atom contentrate was 34.7% by mass.

From the results of the dynamic mechanical analysis by tensile modeusing a hot-press sheet having a thickness of 0.37 mm, the flat variableregion of the storage modulus or the loss modulus was not seen in thetemperature region of the glass transition temperature or higher, thestorage modulus and the loss modulus in the range from 48° C. to 57° C.were from 92.3 to 0.11 MPa and from 97.1 to 0.13 MPa, respectively, andthe change in the storage modulus and the change in the loss moduluswith respect to the temperature were −10.2 MPa/° C. and −10.8 MPa/° C.,respectively.

Subsequently, 23 mg of a solution in whichpoly(1-trifluoromethyl-3,5-cyclopentylene ethylene) thus obtained wasdissolved at a concentration of 20% by mass in cyclohexanone was addeddropwise onto the pattern of the mold A, and uniformly coated by barcoating. It was dried at room temperature for 30 minutes under nitrogengas flow, and then dried at 180° C. for 30 minutes. The mold was cooledto 5° C. under nitrogen, followed by performing the peeling from themold, to obtain an imprint product in the form of a film having a filmthickness of 7 μm and a fine pattern transcribed thereon. The patternwas observed by means of SEM, and found to be in the shape of adistorted line with L1=569 to 598 nm.

Comparative Example 3 Production of Imprint Product Using Coating Liquidof Composition Including Poly(1-Trifluoromethyl-3,5-CyclopentyleneEthylene) and UV-Curable Resin

To 5 g of a solution in whichpoly(1-trifluoromethyl-3,5-cyclopentyleneethylene) with Mw=98000synthesized in Comparative Example 2 was dissolved at a concentration of27% by mass in cyclohexanone was added 1.35 g of a solution including1.0% by mass of the UV-curable resin monomer and 0.03% by mass of thephotopolymerization initiator, each described in Example 4, in2-methoxyethanol, and 20 mg of the solution thus obtained was addeddropwise onto the pattern of the mold A and uniformly coated by spincoating.

Subsequently, it was dried at room temperature for 30 minutes undernitrogen gas flow, and then dried at 180° C. for 30 minutes. The curableresin was cured with UV irradiation at a light quantity of 500 mJ/cm²,and then peeled from the mold to obtain an imprint product in the formof a film having a film thickness of 9 μm and a fine pattern transcribedthereon. The pattern was observed by means of SEM, and found to be inthe shape of a distorted line with L1=570 to 592 nm.

Comparative Example 4

Production of imprint product with UV-curable resin 30 mg of a solutionin which the UV-curable resin monomer and the photopolymerizationinitiator, each described in Example 5 were dissolved at concentrationsof 30% by mass and 0.9% by mass, respectively, in 2-methoxyethanol wasadded dropwise onto the pattern of the mold A, and uniformly coated byspin coating.

Subsequently, it was dried at room temperature for 30 minutes undernitrogen gas flow, then dried at 180° C. for 30 minutes, and was cooledto room temperature. After the curable resin was cured with UVirradiation at a light quantity of 500 mJ/cm², peeling it from the moldwas tried but it could not be done since the film was brittle and thus,cracked. Furthermore, the pencil hardness of the film having thesolution coated on the glass substrate was equal to or higher than 9H,and the average transmittance at 345 to 385 nm of the peeled film havinga thickness of 9 μm was 83.2%.

INDUSTRIAL APPLICABILITY

An imprint product obtained from the fluorine-containing cyclic olefinpolymer composition of the present invention including afluorine-containing cyclic olefin polymer (A) having a specificstructure, a photocurable compound (B), and a photocuring initiator (C)is useful as an imprint product itself or as a replica mold in ananoimprint method, and is of a high industrial value. An imprintproduct having a fine pattern obtained using the production method ofthe present invention, or a cured product produced using the imprintproduct as a replica mold are useful as an optical element (a micro lensarray, an optical waveguide, an optical switching, a Fresnel zone plate,a binary optical element, a blaze optical element, a photonics crystal,or the like), an anti-reflection filter, a biochip, a microreactor chip,a recording medium, a display material, a carrier for a catalyst, or thelike.

The present invention may include the following embodiments.

(a) A fluorine-containing cyclic olefin polymer composition, including afluorine-containing cyclic olefin polymer (A) containing a repeatingstructural unit represented by the general formula (1) and having afluorine atom content rate of 40 to 75% by mass; a photocurable compound(B); and a photocuring initiator (C).

(in the formula (1), R¹ to R⁴ are selected from the group consisting offluorine, fluorine-containing alkyl having 1 to 10 carbon atoms,hydrogen, and alkyl having 1 to 10 carbon atoms, and at least one of R¹to R⁴ is fluorine or fluorine-containing alkyl having 1 to 10 carbonatoms; R¹ to R⁴ may be combined with one another to form a ringstructure.)

(b) The fluorine-containing cyclic olefin polymer composition asdescribed in (a),

wherein the mass ratio (A)/(B) of the fluorine-containing cyclic olefinpolymer (A) and the photocurable compound (B) is in the range from99.9/0.1 to 80.0/20.0.

(c) The fluorine-containing cyclic olefin polymer composition asdescribed in (a) or (b),

wherein the fluorine-containing cyclic olefin polymer (A) is afluorine-containing cyclic olefin polymer having a region in which thechange in the storage modulus or loss modulus with respect to the changein the temperature in the temperature region equal to or higher than theglass transition temperature is from −1 to 0 MPa/° C.

(d) The fluorine-containing cyclic olefin polymer composition asdescribed in (c),

wherein the fluorine-containing cyclic olefin polymer (A) is afluorine-containing cyclic olefin polymer in which the flat variableregion of the storage modulus or the loss modulus in the temperature inthe temperature region equal to or higher than the glass transitiontemperature is in the storage modulus or loss modulus region of 0.1 MPaor more.

(e) An imprint product to which a fine pattern of a mold is transcribed,obtained by bringing the fluorine-containing cyclic olefin polymercomposition as described in any one of (a) to (d) into contact with themold surface of a mold having a fine pattern over its surface,irradiating it with light to perform curing, and then transcribing thefine pattern of the mold surface.

(f) A method for producing an imprint product, comprising bringing thefluorine-containing cyclic olefin polymer composition as described inany one of (a) to (d) into contact with a mold having a fine patternformed over its surface, heating and irradiating with light to performcuring, transcribing the pattern of the mold.

(g) A method for producing a cured product having a fine patterntranscribed over its surface, obtained by bringing the surface havingthe fine pattern of the imprint product as described in (e) into contactwith a photocurable monomer composition, irradiating with light toperform curing, and then releasing the imprint product.

The invention claimed is:
 1. An imprint product having a fine pattern ofa mold surface transcribed, wherein the imprint product comprises: afluorine-containing cyclic olefin polymer (A) containing a repeatingstructural unit represented by the general formula (1) and having afluorine atom content rate of 40 to 75% by mass; a photocurable compound(B); and a photocuring initiator (C);

wherein, at least one of R¹ to R⁴ is fluorine, fluorine-containing alkylhaving 1 to 10 carbon atoms, fluorine-containing alkoxy having 1 to 10carbon atoms, or fluorine-containing alkoxyalkyl having 2 to 10 carbonatoms; wherein when R¹ to R⁴ are fluorine-free groups, R¹ to R⁴ areselected from hydrogen, alkyl having 1 to 10 carbon atoms, alkoxy having1 to 10 carbon atoms, and alkoxyalkyl having 2 to 10 carbon atoms; R¹ toR⁴ are the same as or different from each other; R¹ to R⁴ are optionallycombined with one another to form a ring structure; wherein the massratio (A)/(B) of said fluorine-containing cyclic olefin polymer (A) andsaid photocurable compound (B) is in the range from 99.9/0.1 to 80/20and wherein said photocurable compound (B) is a (meth)acrylate monomerhaving a trifunctional or higher reactive double bond group and/or anepoxy monomer having a trifunctional or higher cationically ring-openingpolymerizable linking group.
 2. The imprint product as set forth inclaim 1, wherein the storage modulus or loss modulus of saidfluorine-containing cyclic olefin polymer (A) in the measurement of adynamic mechanical analysis by tensile mode at a frequency of 1 Hz and atemperature increase rate of 3° C./minute has a variable region in therange from −1 to 0 MPa/° C. with respect to a temperature varying in thetemperature region of the glass transition temperature or higher.
 3. Theimprint product as set forth in claim 1, wherein the variable region ofthe storage modulus or loss modulus in the temperature region of theglass transition temperature or higher of said fluorine-containingcyclic olefin polymer (A) is in the storage modulus region or lossmodulus region of 0.1 MPa or more.
 4. The imprint product as set forthin claim 1, wherein said fluorine-containing cyclic olefin polymer (A)comprises a repeating structural unit [I] represented by the generalformula (1) and a repeating structural unit [II] represented by thegeneral formula (2), the molar ratio thereof is [I]/[II]=95/5 to 25/75,and the fluorine atom content rate is 40 to 75% by mass;

wherein at least one of R⁵ to R⁸ is fluorine, fluorine-containing alkylhaving 1 to 10 carbon atoms, fluorine-containing alkoxy having 1 to 10carbon atoms, or fluorine-containing alkoxyalkyl having 2 to 10 carbonatoms; wherein when R⁵ to R⁸ are fluorine-free groups, R⁵ to R⁸ areselected from hydrogen, alkyl having 1 to 10 carbon atoms, alkoxy having1 to 10 carbon atoms, and alkoxyalkyl having 2 to 10 carbon atoms; R⁵ toR⁸ are the same as or different from each other; R⁵ to R⁸ are optionallycombined with one another to form a ring structure; n represents aninteger of 1 or
 2. 5. The imprint product as set forth in claim 1,wherein said photocurable compound (B) is at least one compound selectedfrom the group of compounds represented by the following generalformulae (5), (6), (7), (8) and (9);

wherein, in the formula (5), R¹² represents tolylene, diphenylmethane,hexamethylene, norbornane dimethylene, dicyclohexylenemethane,trimethylcyclohexylene, cyclohexane dimethylene,N,N′,N″-tris(hexamethylene)-isocyanurate, N,N′-dihexamethyleneurea,N,N,N′-tris(hexamethylene)-urea, N,N,N′,N′-tetrakis(hexamethylene)-urea,or xylene; R⁹, R¹⁰, and R¹¹ independently represent H or CH₃; W¹ and W²represent H, CH₃, OH, or V¹; X¹ represents an integer of 2 to 4; Y¹represents an integer of 0 to 2 and Y² represents an integer of 0 to 5;

wherein, in the formula (6), R¹⁶ represents tolylene, diphenyl methane,hexamethylene, norbornanedimethylene, dicyclohexylenemethane,trimethylcyclohexylene, cyclohexane dimethylene,N,N′,N″-tris(hexamethylene)-isocyanurate, N,N′-dihexamethyleneurea,N,N,N′-tris(hexamethylene)-urea, N,N,N′,N′-tetrakis(hexamethylene)-urea,or xylene; R¹³, R¹⁴, and R¹⁵ independently represent H or CH₃; W³ and W⁴represent H, CH₃, OH, or V²; X² represents an integer of 2 to 4; Y³represents an integer of 0 to 2 and Y⁴ represents an integer of 0 to 5;

wherein, in the formula (7), W⁵ represents H, CH₃, OH, or V³; R¹⁷, R¹⁸,and R¹⁹ independently represent H or CH₃, and Y⁵ represents an integerof 0 to 20;

wherein, in the formula (8), W⁶ and W⁷ represent H, CH₃, OH, or V⁴; R²⁰,R²¹, and R²² represent H or CH₃, and Y⁶ represents an integer of 0 to 3;

wherein, in the formula (9), W⁸ represents H, alkyl having 1 to 3 carbonatoms, OH, or V⁵, and Y⁷ represents an integer of 1 to
 20. 6. A methodfor producing a cured body using the imprint product as set forth inclaim 1 as a mold, wherein the method comprises a step of bringing asurface having the fine pattern of said imprint product into contactwith a photocurable monomer composition, a step of curing saidphotocurable monomer composition with light irradiation to obtain acured product, and a step of releasing said cured product from saidimprint product.
 7. A resin composition for obtaining imprint producttranscribed a fine pattern of a mold surface, wherein the compositioncomprising: a fluorine-containing cyclic olefin polymer (A) containing arepeating structural unit represented by the general formula (1) andhaving a fluorine atom content rate of 40 to 75% by mass; a photocurablecompound (B); and a photocuring initiator (C);

wherein, at least one of R¹ to R⁴ is fluorine, fluorine-containing alkylhaving 1 to 10 carbon atoms, fluorine-containing alkoxy having 1 to 10carbon atoms, or fluorine-containing alkoxyalkyl having 2 to 10 carbonatoms; wherein when R¹ to R⁴ are fluorine-free groups, R¹ to R⁴ areselected from hydrogen, alkyl having 1 to 10 carbon atoms, alkoxy having1 to 10 carbon atoms, and alkoxyalkyl having 2 to 10 carbon atoms; R¹ toR⁴ are the same as or different from each other; R¹ to R⁴ are optionallycombined with one another to form a ring structure; wherein the massratio (A)/(B) of said fluorine-containing cyclic olefin polymer (A) andsaid photocurable compound (B) is in the range from 99.9/0.1 to 80/20and wherein said photocurable compound (B) is a (meth)acrylate monomerhaving a trifunctional or higher reactive double bond group and/or anepoxy monomer having a trifunctional or higher cationically ring-openingpolymerizable linking group.
 8. The resin composition for transcriptionas set forth in claim 7, wherein the mass ratio (A)/(B) of saidfluorine-containing cyclic olefin polymer (A) and said photocurablecompound (B) is in the range from 99.9/0.1 to 80/20.
 9. The resincomposition for transcription as set forth in claim 7, wherein thestorage modulus or loss modulus of said fluorine-containing cyclicolefin polymer (A) in the measurement of a dynamic mechanical analysisby tensile mode at a frequency of 1 Hz and a temperature increase rateof 3° C./minute has a variable region in the range from −1 to 0 MPa/° C.with respect to a temperature varying in the temperature region of theglass transition temperature or higher.
 10. The resin composition fortranscription as set forth in claim 7, wherein the variable region ofthe storage modulus or loss modulus in the temperature region of theglass transition temperature or higher of said fluorine-containingcyclic olefin polymer (A) is in the storage modulus region or lossmodulus region of 0.1 MPa or more.
 11. The resin composition fortranscription as set forth in claim 7, wherein said fluorine-containingcyclic olefin polymer (A) comprises a repeating structural unit [I]represented by said general formula (1) and a repeating structural unit[II] represented by the general formula (2), the molar ratio of both therepeating structural units is [I]/[II]=95/5 to 25/75, and the fluorineatom content rate is 40 to 75% by mass;

wherein, at least one of R⁵ to R⁸ is fluorine, fluorine-containing alkylhaving 1 to 10 carbon atoms, fluorine-containing alkoxy having 1 to 10carbon atoms, or fluorine-containing alkoxyalkyl having 2 to 10 carbonatoms; wherein when R⁵ to R⁸ are fluorine-free groups, R⁵ to R⁸ areselected from hydrogen, alkyl having 1 to 10 carbon atoms, alkoxy having1 to 10 carbon atoms, and alkoxyalkyl having 2 to 10 carbon atoms; R⁵ toR⁸ are the same as or different from each other; R⁵ to R⁸ are optionallycombined with one another to form a ring structure; n represents aninteger of 1 or 2.